CN104843680A - Method for batch preparation of graphene from microcrystalline graphite - Google Patents
Method for batch preparation of graphene from microcrystalline graphite Download PDFInfo
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Abstract
The invention relates to a method for batch preparation of graphene from microcrystalline graphite, and belongs to the technical field of graphene material preparation. The method comprises the following steps: uniformly mixing microcrystalline graphite powder with a surfactant and a solvent 1 to the concentration of the microcrystalline graphite of 0.1-5mg.mL<-1>; carrying out ultrasonic treatment under an ultrasonic power of 200-3200W for 5-20h; carrying out crushing peeling in a vortex crusher with the power of 4000-6000W for 5-12h; carrying out ultrasonic treatment under the ultrasonic power of 200-3200W at 0-5DEG C for 5-20h; centrifuging, and collecting the obtained precipitate; dispersing the precipitate in a solvent 2, centrifuging, and collecting the new precipitate; dispersing the new precipitate, centrifuging, and collecting the finally obtained precipitate; and dispersing the finally obtained precipitate in water, freezing within 10min to form a solid, and carrying out vacuum drying to obtain microcrystalline graphene. The method has the advantages of simplicity, reliability, low cost and abundant reserve of the raw material microcrystalline graphite, and suitableness for batch production.
Description
Technical field
The present invention relates to a kind of method being prepared Graphene by micro crystal graphite batch, specifically, relate to a kind of can in the mixing solutions of close solvent and tensio-active agent with graphenic surface, peel off micro crystal graphite to prepare the method for micro crystal graphite alkene, described method is ultrasonic and pulverizes stripping method, belongs to grapheme material preparing technical field.
Background technology
Graphene is the thinnest in the world at present, the hardest nano material, it has good conductivity, physical strength is high, specific surface area is large, bent, good and the chemically stable advantages of higher of light transmission, can be used on ultralight flak jackets, ultra-thin and ultra-light type aircraft materials, supercoat, microelectronic (as: may become the substitute of silicon, manufacture superminiature transistor, be used for producing following supercomputer, the electronic mobility that carbon is higher can make following computer obtain higher speed) and new energy field (as: ultracapacitor, lithium ion battery) etc. aspect.
The method preparing Graphene is at present very many, mainly includes machine synthesis method, chemical Vapor deposition process, epitaxial growth method, organic synthesis method and oxidation reduction process etc.Wherein, the preparation process complexity of organic synthesis method is loaded down with trivial details, and the cycle is long, is difficult to large-scale production; Chemical Vapor deposition process is comparatively ripe, can realize continuous seepage, but product subsequent transfer usually can by substrate contamination; The graphene film that epitaxial growth method obtains is even, but needs hot conditions, and pattern is difficult to control; Although mechanically peel method is simple, output is extremely low, can not meet the requirement of suitability for industrialized production; Oxidation reduction process can prepare Graphene in a large number, it is the method preparing Graphene the most frequently used at present, but, oxidation reduction process relates to chemical oxidation and intercalation process, the defect on graphene sheet layer can be caused more, cause the performance having a strong impact on Graphene, as electroconductibility, thermal conductivity, chemical stability etc., thus the application affecting Graphene.Therefore, urgently develop a kind of simple effectively and the method for high-quality graphene can be prepared in batches.
It is crystalline flake graphite that current batch is prepared Graphene method raw materials used, and China's micro crystal graphite reserves are up to 2,000,000,000 tons, are micro crystal graphite producing countries maximum in the world, but very limited to the R and D of micro crystal graphite, usually with material outlet.Along with the overexploitation of China's high-quality graphite, research and development micro crystal graphite is extremely urgent.
Summary of the invention
For the defect that prior art exists, the object of the present invention is to provide a kind of method being prepared Graphene by micro crystal graphite batch, specifically, relate to a kind of in the solvent close with graphenic surface energy and tensio-active agent, micro crystal graphite is peeled off by excusing from death, pulverizing the method preparing micro crystal graphite alkene, and described method can utilize the micro crystal graphite resource of China's abundant, and preparation process is simple, with low cost, can be mass-produced.
Object of the present invention is realized by following technical scheme.
Prepared a method for Graphene by micro crystal graphite batch, described method steps is as follows:
(1) mixed by micro crystal graphite powder, tensio-active agent and solvent 1, obtain the suspension liquid 1 of black, wherein, the concentration of micro crystal graphite is 0.1mg mL
-1~ 5mg mL
-1;
Wherein, tensio-active agent is cetyl trimethylammonium bromide, sodium lauryl sulphate, sodium laurylsulfate or polyvinylpyrrolidone; Solvent 1 is the mixing solutions of organic reagent and orthodichlorobenzene, and described organic reagent is N-Methyl pyrrolidone, DMF, N,N-dimethylacetamide and butyrolactone wherein one or more; The volume ratio of preferred organic reagent and orthodichlorobenzene is 3:1 ~ 1:3; Preferred mixing 2h ~ 12h, mixing can adopt magnetic agitation; Micro crystal graphite is 10:1 ~ 20:1 with the ratio of surfactant qualities;
(2) suspension liquid 1 supersound process 5h ~ 20h step (1) obtained, ultrasonic power is 200W ~ 3200W, obtains the suspension liquid 2 of black;
(3) suspension liquid 2 step (2) obtained is in eddy current type crusher, carry out pulverizing and peel off 5h ~ 12h, the power of described eddy current type crusher is 4000W ~ 6000W, obtains the suspension liquid 3 of black, wherein containing the micro crystal graphite alkene of less than 7 layers;
(4) suspension liquid 3 step (3) obtained supersound process 5h ~ 20h in 0 DEG C ~ 5 DEG C, ultrasonic power is 200W ~ 3200W, obtains the suspension liquid 4 of black;
Supersound process can be carried out in ice-water bath;
(5) suspension liquid 4 centrifugation step (4) obtained, collects lower sediment, is precipitated 1;
The rotating speed of preferred described centrifugation is 8000 revs/min ~ 11000 revs/min, centrifugal 15min ~ 60min;
(6) precipitation 1 that step (5) obtains is distributed in solvent 2 forms homogeneous suspension liquid 5, centrifugation, collect lower sediment, be precipitated 2;
Described solvent 2 is dehydrated alcohol, methyl alcohol, Virahol or n-propyl alcohol;
Centrifugation is carried out after preferred ultrasonic disperse; The rotating speed of preferred described centrifugation is 7000 revs/min ~ 11000 revs/min, centrifugal 10min ~ 30min; Preferred steps (6) carries out >=2 times;
(7) precipitation 2 that step (6) obtains is distributed in water forms homogeneous suspension liquid 6, centrifugation, collect lower sediment, be precipitated 3;
The purity of preferably water is the water of more than distilled water purity; Centrifugation is carried out after preferred ultrasonic disperse; The rotating speed of preferred described centrifugation is 7000 revs/min ~ 10000 revs/min, centrifugal 10min ~ 30min; Preferred steps (7) carries out >=2 times;
(8) precipitation 3 that step (7) obtains is distributed in water forms homogeneous suspension liquid 7, suspension liquid 7 is frozen into solid at≤10min, then carries out vacuum-drying, obtains micro crystal graphite alkene;
Preferably water is the water more than distilled water purity; Preferred ultrasonic disperse, ultrasonic power is 200W ~ 1000W, ultrasonic 10min ~ 30min; Preferred employing liquid nitrogen carries out freezing.
Beneficial effect
1. the invention provides a kind of method being prepared Graphene by micro crystal graphite batch, described method is simple, reliable, and starting material micro crystal graphite cost used is low, margin abundant and applicable batch production;
2. the invention provides a kind of method being prepared Graphene by micro crystal graphite batch, the micro crystal graphite alkene that described method micro crystal graphite is prepared as raw material raw material, there is the small size that Graphene prepared by crystalline flake graphite on market does not possess, the feature that surface-area is large and electronic conductivity is high, energy storage and the transition material of good properties can be developed, can be used as the electrode materials of ultracapacitor, lithium ion battery, fuel-cell catalyst and senior electrically conductive ink etc.;
3. the invention provides a kind of method being prepared Graphene by micro crystal graphite batch, micro crystal graphite alkene prepared by described method can be used to improve the multifunctionality of matrix material and the processing characteristics etc. of matrix material, the matrix material of physics, chemistry and mechanical property that preparation is unique, for matrix material provides more wide Application Areas, realize the multifunction application of Graphene;
4. the invention provides a kind of method being prepared Graphene by micro crystal graphite batch, in described method: the object of step (2) is micro crystal graphite to carry out part stripping, form micro crystal graphite thin compared with raw material micro crystal graphite; The object of step (3) is that the micro crystal graphite thin compared with raw material step (2) obtained peels off into the micro crystal graphite alkene of less than 7 layers further; In step (4) in 0 DEG C ~ 5 DEG C supersound process, prevent temperature too high make micro crystal graphite alkene reunite or again stacking, the object of step (4) is that step (3) is not peeled off micro crystal graphite completely peels off into micro crystal graphite alkene further; In step (5) reclaim supernatant liquid as solvent 1, the stripping for next batch micro crystal graphite uses; Supernatant liquid reclaims and uses as solvent 2 by step (6), and the object of step (6) is to wash away solvent 1 residual in micro crystal graphite alkene; The object of step (7) is to wash away solvent 2 residual in micro crystal graphite alkene.
Accompanying drawing explanation
Fig. 1 is the X-ray powder diffraction test result figure of the final product obtained in embodiment 1.
Fig. 2 is the scanning electronic microscope detected result figure of the final product obtained in embodiment 1.
Fig. 3 is the transmission electron microscope detected result figure of the final product obtained in embodiment 1.
The transmission electron microscope detected result figure of Fig. 4 to be the resolving power of the final product obtained in embodiment 1 be 0.2nm.
Fig. 5 is the selected area electron diffraction figure of the final product obtained in embodiment 1.
Embodiment
For better understanding the present invention, below in conjunction with specific embodiment, the present invention is described in further detail, but is not limited thereto.
The producer of the crusher of eddy current type described in following examples is: Xian Chang ultrasonic equipment company limited, model is: XC-CD-1800.
Embodiment 1
Prepared a method for Graphene by micro crystal graphite batch, described method steps is as follows:
(1) 0.1g micro crystal graphite powder, 0.01g cetyl trimethylammonium bromide are mixed with solvent 1 magnetic agitation 2h in beaker of 1000mL, obtain the suspension liquid 1 of black, wherein, the concentration of micro crystal graphite is 0.1mg mL
-1; Described solvent 1 is mixed with volume ratio 1:1 by N-Methyl pyrrolidone and orthodichlorobenzene;
(2) suspension liquid 1 supersound process 5h step (1) obtained, ultrasonic power is 200W, obtains the suspension liquid 2 of black;
(3) suspension liquid 2 step (2) obtained is pulverized and is peeled off 5h in eddy current type crusher, and the power of eddy current type crusher is 4000W, obtains the suspension liquid 3 of black;
(4) the suspension liquid 3 supersound process 5h in ice-water bath step (3) obtained, ultrasonic power is 200W, obtains the suspension liquid 4 of black;
(5) be transferred in the centrifuge tube of 50mL by the suspension liquid 4 that step (4) obtains, with the centrifugal 15min of the rotating speed of 11000 revs/min, reclaimed by supernatant liquid, the stripping for next batch micro crystal graphite uses, and collects lower sediment, is precipitated 1;
(6) precipitation 1 that step (5) obtains is added in the dehydrated alcohol of 500mL, the homogeneous suspension liquid 5-1 obtained after ultrasonic disperse, is transferred in the centrifuge tube of 50mL, with the centrifugal 20min of the rotating speed of 7000 revs/min, supernatant liquid is reclaimed, collects lower sediment; Repeat described operation more once, the lower sediment of collecting by this step adds in the dehydrated alcohol of 500mL, the homogeneous suspension liquid 5-2 obtained after ultrasonic disperse, be transferred in the centrifuge tube of 50mL, with the centrifugal 20min of the rotating speed of 7000 revs/min, supernatant liquid is reclaimed, collects lower sediment, be precipitated 2;
(7) precipitation 2 that step (6) obtains is added in the distilled water of 500mL, after ultrasonic disperse, obtain homogeneous suspension liquid 6-1, be transferred in the centrifuge tube of 50mL, with the centrifugal 30min of the rotating speed of 7000 revs/min, outwell supernatant liquid, collect lower sediment; Repeat described operation more once, the lower sediment of collecting by this step adds in the distilled water of 500mL, homogeneous suspension liquid 6-2 is obtained after ultrasonic disperse, be transferred in the centrifuge tube of 50mL, with the centrifugal 30min of the rotating speed of 7000 revs/min, outwell supernatant liquid, collect lower sediment, be precipitated 3;
(8) precipitation 3 that step (7) obtains is added in the distilled water of 10mL, homogeneous suspension liquid 7 is obtained after ultrasonic disperse 10min, ultrasonic power is 200W, suspension liquid 7 is frozen into solid in liquid nitrogen, then room temperature in vacuo is dry, vacuum tightness is 8 ~ 12MPa, obtains final product.
The final product obtained is detected as follows:
(1) X-ray powder diffraction test: as shown in Figure 1, can see the characteristic peak 25 ° of micro crystal graphite alkene, illustrate that micro crystal graphite is transformed to micro crystal graphite alkene, final product is micro crystal graphite alkene to result;
(2) x-ray photoelectron power spectrum test: result shows that the element ratio of C/O in final product is 9.7, illustrates that the Graphene oxygen level in final product is few;
(3) Raman spectrum test: result display is respectively at about 1350cm
-1and 1590cm
-1there is the D band of Graphene and the characteristic peak of E band in place, D peak represents SP
3the vibration absorption peak of the one-tenth key model of hydridization carbon, as: " C-C ", " C-O ", " C=O ", " O-C=O ", the area ratio of E band and D band is 10.5, illustrates that the defect of final product is little;
(4) microscopic examination: scanning electronic microscope result as shown in Figure 2, transmission electron microscope result as shown in Figure 3, from Fig. 2,3, the structure of final product is laminar structured, size in tens nanometers to hundreds of nanometer not etc., in conjunction with resolving power be the Electron Microscopy Results of 0.2nm as shown in Figure 4, selected area electron diffraction figure result as shown in Figure 5, and atomic force microscope test pattern, the sheet number of plies of known final product is respectively 2,4 and 7 layers, all≤7 layers.
Embodiment 2
Prepared a method for Graphene by micro crystal graphite batch, described method steps is as follows:
(1) 12g micro crystal graphite powder, 0.6g sodium lauryl sulphate are mixed with solvent 1 magnetic agitation 6h in beaker of 5000mL, obtain the suspension liquid 1 of black, wherein, the concentration of micro crystal graphite is 2.4mgmL
-1; Described solvent 1 is mixed with volume ratio 1:3 by DMF and orthodichlorobenzene;
(2) suspension liquid 1 supersound process 12h step (1) obtained, ultrasonic power is 2000W, obtains the suspension liquid 2 of black;
(3) suspension liquid 2 step (2) obtained is pulverized and is peeled off 8h in eddy current type crusher, and the power of eddy current type crusher is 5000W, obtains the suspension liquid 3 of black;
(4) the suspension liquid 3 supersound process 12h in ice-water bath step (3) obtained, ultrasonic power is 2000W, obtains the suspension liquid 4 of black;
(5) be transferred in the centrifuge tube of 300mL by the suspension liquid 4 that step (4) obtains, with the centrifugal 40min of the rotating speed of 9000 revs/min, reclaimed by supernatant liquid, the stripping for next batch micro crystal graphite uses, and collects lower sediment, is precipitated 1;
(6) precipitation 1 that step (5) obtains is added in the anhydrous n-propyl alcohol of 1500mL, the homogeneous suspension liquid 5-1 obtained after ultrasonic disperse, is transferred in the centrifuge tube of 300mL, with the centrifugal 10min of the rotating speed of 11000 revs/min, supernatant liquid is reclaimed, collects lower sediment; Repeat described operation more once, the lower sediment of collecting by this step adds in the anhydrous n-propyl alcohol of 1500mL, the homogeneous suspension liquid 5-2 obtained after ultrasonic disperse, be transferred in the centrifuge tube of 300mL, with the centrifugal 10min of the rotating speed of 11000 revs/min, supernatant liquid is reclaimed, collects lower sediment, be precipitated 2;
(7) precipitation 2 that step (6) obtains is added in the distilled water of 1500mL, after ultrasonic disperse, obtain homogeneous suspension liquid 6-1, be transferred in the centrifuge tube of 300mL, with the centrifugal 30min of the rotating speed of 9000 revs/min, outwell supernatant liquid, collect lower sediment; Repeat described operation more once, the lower sediment of collecting by this step adds in the distilled water of 1500mL, homogeneous suspension liquid 6-2 is obtained after ultrasonic disperse, be transferred in the centrifuge tube of 300mL, with the centrifugal 30min of the rotating speed of 9000 revs/min, outwell supernatant liquid, collect lower sediment, be precipitated 3;
(8) precipitation 3 that step (7) obtains is added the distilled water of 80mL, homogeneous suspension liquid 7 is obtained after 20min after ultrasonic disperse, ultrasonic power is 500W, suspension liquid 7 is frozen into solid in liquid nitrogen, then room temperature in vacuo is dry, vacuum tightness is 8 ~ 12MPa, obtains final product.
The final product obtained is detected as follows:
(1) X-ray powder diffraction test: as shown in Figure 1, can see the characteristic peak 25 ° of micro crystal graphite alkene, illustrate that micro crystal graphite is transformed to micro crystal graphite alkene, final product is micro crystal graphite alkene to result;
(2) x-ray photoelectron power spectrum test: result shows that the element ratio of C/O in final product is 9.9, illustrates that the Graphene oxygen level in final product is few;
(3) Raman spectrum test: result display is respectively at about 1350cm
-1and 1590cm
-1there is the D band of Graphene and the characteristic peak of E band in place, D peak represents SP
3the vibration absorption peak of the one-tenth key model of hydridization carbon, as: " C-C ", " C-O ", " C=O ", " O-C=O ", the area ratio of E band and D band is 11.5, illustrates that the defect of final product is little;
(4) microscopic examination: from scanning electronic microscope and transmission electron microscope result, the structure of final product is laminar structured, size is not in tens nanometers to hundreds of nanometer etc., be the Electron Microscopy Results of 0.2nm, selected area electron diffraction figure result and atomic force microscope test result in conjunction with resolving power, the sheet number of plies of known final product all≤7 layers.
Embodiment 3
Prepared a method for Graphene by micro crystal graphite batch, described method steps is as follows:
(1) 10g micro crystal graphite powder, 1g sodium laurylsulfate are mixed with solvent 1 magnetic agitation 12h in beaker of 2000mL, obtain the suspension liquid 1 of black, wherein, the concentration of micro crystal graphite is 5mgmL
-1; Described solvent 1 is mixed with volume ratio 1:2 by N,N-dimethylacetamide and orthodichlorobenzene;
(2) suspension liquid 1 supersound process 20h step (1) obtained, ultrasonic power is 3200W, obtains the suspension liquid 2 of black;
(3) suspension liquid 2 step (2) obtained is pulverized and is peeled off 12h in eddy current type crusher, and the power of eddy current type crusher is 6000W, obtains the suspension liquid 3 of black;
(4) the suspension liquid 3 supersound process 20h in 0 DEG C of ice-water bath step (3) obtained, ultrasonic power is 3200W, obtains the suspension liquid 4 of black;
(5) be transferred in the centrifuge tube of 300mL by the suspension liquid 4 that step (4) obtains, with the centrifugal 60min of the rotating speed of 9000 revs/min, reclaimed by supernatant liquid, the stripping for next batch micro crystal graphite uses, and collects lower sediment, is precipitated 1;
(6) precipitation 1 that step (5) obtains is added in the anhydrous isopropyl alcohol of 2500mL, the homogeneous suspension liquid 5-1 obtained after ultrasonic disperse, is transferred in the centrifuge tube of 300mL, with the centrifugal 30min of the rotating speed of 9000 revs/min, supernatant liquid is reclaimed, collects lower sediment; Repeat described operation more once, the lower sediment of collecting by this step adds in the anhydrous isopropyl alcohol of 2500mL, the homogeneous suspension liquid 5-2 obtained after ultrasonic disperse, be transferred in the centrifuge tube of 300mL, with the centrifugal 30min of the rotating speed of 9000 revs/min, supernatant liquid is reclaimed, collects lower sediment, be precipitated 2;
(7) precipitation 2 that step (6) obtains is added in the distilled water of 2500mL, after ultrasonic disperse, obtain homogeneous suspension liquid 6-1, be transferred in the centrifuge tube of 300mL, with the centrifugal 10min of the rotating speed of 10000 revs/min, outwell supernatant liquid, collect lower sediment; Repeat described operation more once, the lower sediment of collecting by this step adds in the distilled water of 2500mL, homogeneous suspension liquid 6-2 is obtained after ultrasonic disperse, be transferred in the centrifuge tube of 300mL, with the centrifugal 10min of the rotating speed of 10000 revs/min, outwell supernatant liquid, collect lower sediment, be precipitated 3;
(8) precipitation 3 that step (7) obtains is added in the distilled water of 120mL, homogeneous suspension liquid 7 is obtained after ultrasonic disperse 20min, ultrasonic power is 800W, suspension liquid 7 is frozen into solid in liquid nitrogen, then room temperature in vacuo is dry, vacuum tightness is 8 ~ 12MPa, obtains final product.
The final product obtained is detected as follows:
(1) X-ray powder diffraction test: as shown in Figure 1, can see the characteristic peak 25 ° of micro crystal graphite alkene, illustrate that micro crystal graphite is transformed to micro crystal graphite alkene, final product is micro crystal graphite alkene to result;
(2) x-ray photoelectron power spectrum test: result shows that the element ratio of C/O in final product is 9.2, illustrates that the Graphene oxygen level in final product is few;
(3) Raman spectrum test: result display is respectively at about 1350cm
-1and 1590cm
-1there is the D band of Graphene and the characteristic peak of E band in place, D peak represents SP
3the vibration absorption peak of the one-tenth key model of hydridization carbon, as: " C-C ", " C-O ", " C=O ", " O-C=O ", the area ratio of E band and D band is 10.9, illustrates that the defect of final product is little;
(4) microscopic examination: from scanning electronic microscope and transmission electron microscope result, the structure of final product is laminar structured, size is not in tens nanometers to hundreds of nanometer etc., be the Electron Microscopy Results of 0.2nm, selected area electron diffraction figure result and atomic force microscope test result in conjunction with resolving power, the sheet number of plies of known final product all≤7 layers.
Embodiment 4
Prepared a method for Graphene by micro crystal graphite batch, described method steps is as follows:
(1) 25g micro crystal graphite powder, 1.5g cetyl trimethylammonium bromide are mixed with solvent 1 magnetic agitation 2h in beaker of 5000mL, obtain the suspension liquid 1 of black, wherein, the concentration of micro crystal graphite is 5mg mL
-1; Described solvent 1 is mixed with volume ratio 3:1 by butyrolactone and orthodichlorobenzene;
(2) suspension liquid 1 supersound process 20h step (1) obtained, ultrasonic power is 3200W, obtains the suspension liquid 2 of black;
(3) suspension liquid 2 step (2) obtained is pulverized and is peeled off 12h in eddy current type crusher, and the power of eddy current type crusher is 6000W, obtains the suspension liquid 3 of black;
(4) the suspension liquid 3 supersound process 20h in 5 DEG C of water-baths step (3) obtained, ultrasonic power is 3200W, obtains the suspension liquid 4 of black;
(5) suspension liquid 4 that step (4) obtains is transferred in the centrifuge tube of 300mL, with the centrifugal 60min of the rotating speed of 11000 revs/min, reclaimed by supernatant liquid, the stripping for next batch micro crystal graphite uses, collect lower sediment, be precipitated 1;
(6) precipitation 1 that step (5) obtains is added in the anhydrous methanol of 2500mL, the homogeneous suspension liquid 5-1 obtained after ultrasonic disperse, is transferred in the centrifuge tube of 300mL, with the centrifugal 30min of the rotating speed of 11000 revs/min, supernatant liquid is reclaimed, collects lower sediment; Repeat described operation more once, the lower sediment of collecting by this step adds in the anhydrous methanol of 2500mL, the homogeneous suspension liquid 5-2 obtained after ultrasonic disperse, be transferred in the centrifuge tube of 300mL, with the centrifugal 30min of the rotating speed of 11000 revs/min, supernatant liquid is reclaimed, collects lower sediment, be precipitated 2;
(7) precipitation 2 that step (6) obtains is added in the distilled water of 2500mL, after ultrasonic disperse, obtain homogeneous suspension liquid 6-1, be transferred in the centrifuge tube of 300mL, with the centrifugal 30min of the rotating speed of 10000 revs/min, outwell supernatant liquid, collect lower sediment; Repeat described operation more once, the lower sediment of collecting by this step adds in the distilled water of 2500mL, homogeneous suspension liquid 6-2 is obtained after ultrasonic disperse, be transferred in the centrifuge tube of 300mL, with the centrifugal 30min of the rotating speed of 10000 revs/min, outwell supernatant liquid, collect lower sediment, be precipitated 3;
(8) precipitation 3 that step (7) obtains is added in the distilled water of 200mL, homogeneous suspension liquid 7 is obtained after ultrasonic disperse 30min, ultrasonic power is 1000W, suspension liquid 7 is frozen into solid in liquid nitrogen, then room temperature in vacuo is dry, vacuum tightness is 8 ~ 12MPa, obtains final product.
The final product obtained is detected as follows:
(1) X-ray powder diffraction test: as shown in Figure 1, can see the characteristic peak 25 ° of micro crystal graphite alkene, illustrate that micro crystal graphite is transformed to micro crystal graphite alkene, final product is micro crystal graphite alkene to result;
(2) x-ray photoelectron power spectrum test: result shows that the element ratio of C/O in final product is 9.8, illustrates that the Graphene oxygen level in final product is few;
(3) Raman spectrum test: result display is respectively at about 1350cm
-1and 1590cm
-1there is the D band of Graphene and the characteristic peak of E band in place, D peak represents SP
3the vibration absorption peak of the one-tenth key model of hydridization carbon, as: " C-C ", " C-O ", " C=O ", " O-C=O ", the area ratio of E band and D band is 11.2, illustrates that the defect of final product is little;
(4) microscopic examination: from scanning electronic microscope and transmission electron microscope result, the structure of final product is laminar structured, size is not in tens nanometers to hundreds of nanometer etc., be the Electron Microscopy Results of 0.2nm, selected area electron diffraction figure result and atomic force microscope test result in conjunction with resolving power, the sheet number of plies of known final product all≤7 layers.
Embodiment 5
Prepared a method for Graphene by micro crystal graphite batch, described method steps is as follows:
(1) 9g micro crystal graphite powder, 0.9g cetyl trimethylammonium bromide are mixed with solvent 1 magnetic agitation 2h in beaker of 3000mL, obtain the suspension liquid 1 of black, wherein, the concentration of micro crystal graphite is 3mg mL
-1; Described solvent 1 is mixed with volume ratio 2:1 by butyrolactone and orthodichlorobenzene;
(2) suspension liquid 1 supersound process 9h step (1) obtained, ultrasonic power is 1600W, obtains the suspension liquid 2 of black;
(3) suspension liquid 2 step (2) obtained is pulverized and is peeled off 10h in eddy current type crusher, and the power of eddy current type crusher is 4500W, obtains the suspension liquid 3 of black;
(4) the suspension liquid 3 supersound process 15h in 3 DEG C of water-baths step (3) obtained, ultrasonic power is 2500W, obtains the suspension liquid 4 of black;
(5) be transferred in the centrifuge tube of 150mL by the suspension liquid 4 that step (4) obtains, with the centrifugal 30min of the rotating speed of 8000 revs/min, reclaimed by supernatant liquid, the stripping for next batch micro crystal graphite uses, and collects lower sediment, is precipitated 1;
(6) precipitation 1 that step (5) obtains is added in the dehydrated alcohol of 2000mL, the homogeneous suspension liquid 5-1 obtained after ultrasonic disperse, is transferred in the centrifuge tube of 150mL, with the centrifugal 30min of the rotating speed of 9000 revs/min, supernatant liquid is reclaimed, collects lower sediment; Repeat described operation more once, the lower sediment of collecting by this step adds in the dehydrated alcohol of 2000mL, the homogeneous suspension liquid 5-2 obtained after ultrasonic disperse, be transferred in the centrifuge tube of 150mL, with the centrifugal 30min of the rotating speed of 9000 revs/min, supernatant liquid is reclaimed, collects lower sediment, be precipitated 2;
(7) precipitation 2 that step (6) obtains is added in the distilled water of 2000mL, after ultrasonic disperse, obtain homogeneous suspension liquid 6-1, be transferred in the centrifuge tube of 150mL, with the centrifugal 10min of the rotating speed of 10000 revs/min, outwell supernatant liquid, collect lower sediment; Repeat described operation more once, the lower sediment of collecting by this step adds in the distilled water of 2000mL, homogeneous suspension liquid 6-2 is obtained after ultrasonic disperse, be transferred in the centrifuge tube of 150mL, with the centrifugal 10min of the rotating speed of 10000 revs/min, outwell supernatant liquid, collect lower sediment, be precipitated 3;
(8) precipitation 3 that step (7) obtains is added in the distilled water of 100mL, homogeneous suspension liquid 7 is obtained after ultrasonic disperse 30min, ultrasonic power is 500W, suspension liquid 7 is frozen into solid in liquid nitrogen, then room temperature in vacuo is dry, vacuum tightness is 8 ~ 12MPa, obtains final product.
The final product obtained is detected as follows:
(1) X-ray powder diffraction test: as shown in Figure 1, can see the characteristic peak 25 ° of micro crystal graphite alkene, illustrate that micro crystal graphite is transformed to micro crystal graphite alkene, final product is micro crystal graphite alkene to result;
(2) x-ray photoelectron power spectrum test: result shows that the element ratio of C/O in final product is 9.3, illustrates that the Graphene oxygen level in final product is few;
(3) Raman spectrum test: result display is respectively at about 1350cm
-1and 1590cm
-1there is the D band of Graphene and the characteristic peak of E band in place, D peak represents SP
3the vibration absorption peak of the one-tenth key model of hydridization carbon, as: " C-C ", " C-O ", " C=O ", " O-C=O ", the area ratio of E band and D band is 10.5, illustrates that the defect of final product is little;
(4) microscopic examination: from scanning electronic microscope and transmission electron microscope result, the structure of final product is laminar structured, size is not in tens nanometers to hundreds of nanometer etc., be the Electron Microscopy Results of 0.2nm, selected area electron diffraction figure result and atomic force microscope test result in conjunction with resolving power, the sheet number of plies of known final product all≤7 layers.
Embodiment 6
Prepared a method for Graphene by micro crystal graphite batch, described method steps is as follows:
(1) 0.5g micro crystal graphite powder, 0.05g polyvinylpyrrolidone are mixed with solvent 1 magnetic agitation 6h in beaker of 1000mL, obtain the suspension liquid 1 of black, wherein, the concentration of micro crystal graphite is 0.5mg mL
-1; Described solvent 1 is mixed with volume ratio 0.5:0.5:1 successively by N-Methyl pyrrolidone, butyrolactone and orthodichlorobenzene;
(2) suspension liquid 1 supersound process 18h step (1) obtained, ultrasonic power is 2400W, obtains the suspension liquid 2 of black;
(3) suspension liquid 2 step (2) obtained is pulverized and is peeled off 9h in eddy current type crusher, and the power of eddy current type crusher is 5500W, obtains the suspension liquid 3 of black;
(4) the suspension liquid 3 supersound process 16h in 2 DEG C of water-baths step (3) obtained, ultrasonic power is 1200W, obtains the suspension liquid 4 of black;
(5) be transferred in the centrifuge tube of 50mL by the suspension liquid 4 that step (4) obtains, with the centrifugal 25min of the rotating speed of 8000 revs/min, reclaimed by supernatant liquid, the stripping for next batch micro crystal graphite uses, and collects lower sediment, is precipitated 1;
(6) precipitation 1 that step (5) obtains is added in the dehydrated alcohol of 800mL, the homogeneous suspension liquid 5-1 obtained after ultrasonic disperse, is transferred in the centrifuge tube of 50mL, with the centrifugal 15min of the rotating speed of 8000 revs/min, supernatant liquid is reclaimed, collects lower sediment; Repeat described operation more once, the lower sediment of collecting by this step adds in the dehydrated alcohol of 800mL, the homogeneous suspension liquid 5-2 obtained after ultrasonic disperse, be transferred in the centrifuge tube of 50mL, with the centrifugal 15min of the rotating speed of 8000 revs/min, supernatant liquid is reclaimed, collects lower sediment, be precipitated 2;
(7) precipitation 2 that step (6) obtains is added in the distilled water of 800mL, after ultrasonic disperse, obtain homogeneous suspension liquid 6-1, be transferred in the centrifuge tube of 50mL, with the centrifugal 10min of the rotating speed of 10000 revs/min, outwell supernatant liquid, collect lower sediment; Repeat described operation more once, the lower sediment of collecting by this step adds in the distilled water of 800mL, homogeneous suspension liquid 6-2 is obtained after ultrasonic disperse, be transferred in the centrifuge tube of 50mL, with the centrifugal 10min of the rotating speed of 10000 revs/min, outwell supernatant liquid, collect lower sediment, be precipitated 3;
(8) precipitation 3 that step (7) obtains is added in the distilled water of 70mL, homogeneous suspension liquid 7 is obtained after ultrasonic disperse 12min, ultrasonic power is 900W, suspension liquid 7 is frozen into solid in liquid nitrogen, then room temperature in vacuo is dry, vacuum tightness is 8 ~ 12MPa, obtains final product.
The final product obtained is detected as follows:
(1) X-ray powder diffraction test: as shown in Figure 1, can see the characteristic peak 25 ° of micro crystal graphite alkene, illustrate that micro crystal graphite is transformed to micro crystal graphite alkene, final product is micro crystal graphite alkene to result;
(2) x-ray photoelectron power spectrum test: result shows that the element ratio of C/O in final product is 10.3, illustrates that the Graphene oxygen level in final product is few;
(3) Raman spectrum test: result display is respectively at about 1350cm
-1and 1590cm
-1there is the D band of Graphene and the characteristic peak of E band in place, D peak represents SP
3the vibration absorption peak of the one-tenth key model of hydridization carbon, as: " C-C ", " C-O ", " C=O ", " O-C=O ", the area ratio of E band and D band is 12.1, illustrates that the defect of final product is little;
(4) microscopic examination: from scanning electronic microscope and transmission electron microscope result, the structure of final product is laminar structured, size is not in tens nanometers to hundreds of nanometer etc., be the Electron Microscopy Results of 0.2nm, selected area electron diffraction figure result and atomic force microscope test result in conjunction with resolving power, the sheet number of plies of known final product all≤7 layers.
Embodiment 7
Prepared a method for Graphene by micro crystal graphite batch, described method steps is as follows:
(1) 1g micro crystal graphite powder, 0.1g cetyl trimethylammonium bromide are mixed with solvent 1 magnetic agitation 5h in beaker of 1000mL, obtain the suspension liquid 1 of black, wherein, the concentration of micro crystal graphite is 1mg mL
-1; Described solvent 1 is mixed with volume ratio 0.5:0.5:2 successively by N-Methyl pyrrolidone, N,N-dimethylacetamide and orthodichlorobenzene;
(2) suspension liquid 1 supersound process 9h step (1) obtained, ultrasonic power is 1000W, obtains the suspension liquid 2 of black;
(3) suspension liquid 2 step (2) obtained is pulverized and is peeled off 7h in eddy current type crusher, and the power of eddy current type crusher is 4800W, obtains the suspension liquid 3 of black;
(4) the suspension liquid 3 supersound process 12h in ice-water bath step (3) obtained, ultrasonic power is 1200W, obtains the suspension liquid 4 of black;
(5) be transferred in the centrifuge tube of 100mL by the suspension liquid 4 that step (4) obtains, with the centrifugal 60min of the rotating speed of 8000 revs/min, reclaimed by supernatant liquid, the stripping for next batch micro crystal graphite uses, and collects lower sediment, is precipitated 1;
(6) precipitation 1 that step (4) obtains is added in the dehydrated alcohol of 1000mL, the homogeneous suspension liquid 5-1 obtained after ultrasonic disperse, is transferred in the centrifuge tube of 50mL, with the centrifugal 10min of the rotating speed of 11000 revs/min, supernatant liquid is reclaimed, collects lower sediment; Repeat described operation more once, the lower sediment of collecting by this step adds in the dehydrated alcohol of 1000mL, the homogeneous suspension liquid 5-2 obtained after ultrasonic disperse, be transferred in the centrifuge tube of 50mL, with the centrifugal 10min of the rotating speed of 11000 revs/min, supernatant liquid is reclaimed, collects lower sediment, be precipitated 2;
(7) precipitation 2 that step (6) obtains is added in the distilled water of 800mL, after ultrasonic disperse, obtain homogeneous suspension liquid 6-1, be transferred in the centrifuge tube of 50mL, with the centrifugal 10min of the rotating speed of 10000 revs/min, outwell supernatant liquid, collect lower sediment; Repeat described operation more once, the lower sediment of collecting by this step adds in the distilled water of 800mL, homogeneous suspension liquid 6-2 is obtained after ultrasonic disperse, be transferred in the centrifuge tube of 50mL, with the centrifugal 10min of the rotating speed of 10000 revs/min, outwell supernatant liquid, collect lower sediment, be precipitated 3;
(8) precipitation 3 that step (7) obtains is added in the distilled water of 20mL, homogeneous suspension liquid 7 is obtained after ultrasonic disperse 5min, ultrasonic power is 400W, suspension liquid 7 is frozen into solid in liquid nitrogen, then room temperature in vacuo is dry, vacuum tightness is 8 ~ 12MPa, obtains final product.
The final product obtained is detected as follows:
(1) X-ray powder diffraction test: as shown in Figure 1, can see the characteristic peak 25 ° of micro crystal graphite alkene, illustrate that micro crystal graphite is transformed to micro crystal graphite alkene, final product is micro crystal graphite alkene to result;
(2) x-ray photoelectron power spectrum test: result shows that the element ratio of C/O in final product is 9.1, illustrates that the Graphene oxygen level in final product is few;
(3) Raman spectrum test: result display is respectively at about 1350cm
-1and 1590cm
-1there is the D band of Graphene and the characteristic peak of E band in place, D peak represents SP
3the vibration absorption peak of the one-tenth key model of hydridization carbon, as: " C-C ", " C-O ", " C=O ", " O-C=O ", the area ratio of E band and D band is 9.8, illustrates that the defect of final product is little;
(4) microscopic examination: from scanning electronic microscope and transmission electron microscope result, the structure of final product is laminar structured, size is not in tens nanometers to hundreds of nanometer etc., be the Electron Microscopy Results of 0.2nm, selected area electron diffraction figure result and atomic force microscope test result in conjunction with resolving power, the sheet number of plies of known final product all≤7 layers.
Embodiment 8
Prepared a method for Graphene by micro crystal graphite batch, described method steps is as follows:
(1) 8g micro crystal graphite powder, 0.6g cetyl trimethylammonium bromide are mixed with solvent 1 magnetic agitation 10h in beaker of 4000mL, obtain the suspension liquid 1 of black, wherein, the concentration of micro crystal graphite is 2mg mL
-1; Described solvent 1 is mixed with volume ratio 1:1:1:1 successively by N-Methyl pyrrolidone, N,N-dimethylacetamide, butyrolactone and orthodichlorobenzene;
(2) suspension liquid 1 supersound process 16h step (1) obtained, ultrasonic power is 2000W, obtains the suspension liquid 2 of black;
(3) suspension liquid 2 step (2) obtained is pulverized and is peeled off 8h in eddy current type crusher, and the power of eddy current type crusher is 5000W, obtains the suspension liquid 3 of black;
(4) the suspension liquid 3 ultrasonic 18h in ice-water bath step (3) obtained, ultrasonic power is 800W, obtains the suspension liquid 4 of black;
(5) be transferred in the centrifuge tube of 200mL by the suspension liquid 4 that step (4) obtains, with the centrifugal 45min of the rotating speed of 9500 revs/min, reclaimed by supernatant liquid, the stripping for next batch micro crystal graphite uses, and collects lower sediment, is precipitated 1;
(6) precipitation 1 that step (5) obtains is added in the dehydrated alcohol of 2000mL, the homogeneous suspension liquid 5-1 obtained after ultrasonic disperse, is transferred in the centrifuge tube of 150mL, with the centrifugal 30min of the rotating speed of 9000 revs/min, supernatant liquid is reclaimed, collects lower sediment; Repeat described operation more once, the lower sediment of collecting by this step adds in the dehydrated alcohol of 2000mL, the homogeneous suspension liquid 5-2 obtained after ultrasonic disperse, be transferred in the centrifuge tube of 150mL, with the centrifugal 30min of the rotating speed of 9000 revs/min, supernatant liquid is reclaimed, collects lower sediment, be precipitated 2;
(7) precipitation 2 that step (6) obtains is added in the distilled water of 1500mL, after ultrasonic disperse, obtain homogeneous suspension liquid 6-1, be transferred in the centrifuge tube of 150mL, with the centrifugal 20min of the rotating speed of 8000 revs/min, outwell supernatant liquid, collect lower sediment; Repeat described operation more once, the lower sediment of collecting by this step adds in the distilled water of 1500mL, homogeneous suspension liquid 6-2 is obtained after ultrasonic disperse, be transferred in the centrifuge tube of 150mL, with the centrifugal 20min of the rotating speed of 8000 revs/min, outwell supernatant liquid, collect lower sediment, be precipitated 3;
(8) precipitation 3 that step (7) obtains is added in the distilled water of 80mL, homogeneous suspension liquid 7 is obtained after ultrasonic disperse 13min, ultrasonic power is 400W, suspension liquid 7 is frozen into solid in liquid nitrogen, then room temperature in vacuo is dry, vacuum tightness is 8 ~ 12MPa, obtains final product.
The final product obtained is detected as follows:
(1) X-ray powder diffraction test: as shown in Figure 1, can see the characteristic peak 25 ° of micro crystal graphite alkene, illustrate that micro crystal graphite is transformed to micro crystal graphite alkene, final product is micro crystal graphite alkene to result;
(2) x-ray photoelectron power spectrum test: result shows that the element ratio of C/O in final product is 9.6, illustrates that the Graphene oxygen level in final product is few;
(3) Raman spectrum test: result display is respectively at about 1350cm
-1and 1590cm
-1there is the D band of Graphene and the characteristic peak of E band in place, D peak represents SP
3the vibration absorption peak of the one-tenth key model of hydridization carbon, as: " C-C ", " C-O ", " C=O ", " O-C=O ", the area ratio of E band and D band is 10.4, illustrates that the defect of final product is little;
(4) microscopic examination: from scanning electronic microscope and transmission electron microscope result, the structure of final product is laminar structured, size is not in tens nanometers to hundreds of nanometer etc., be the Electron Microscopy Results of 0.2nm, selected area electron diffraction figure result and atomic force microscope test result in conjunction with resolving power, the sheet number of plies of known final product all≤7 layers.
Embodiment 9
Prepared a method for Graphene by micro crystal graphite batch, described method steps is as follows:
(1) 20g micro crystal graphite powder, 2g cetyl trimethylammonium bromide are mixed with solvent 1 magnetic agitation 11h in beaker of 5000mL, obtain the suspension liquid 1 of black, wherein, the concentration of micro crystal graphite is 4mg mL
-1; Described solvent 1 is mixed with volume ratio 1:2 by N-Methyl pyrrolidone and orthodichlorobenzene;
(2) suspension liquid 1 supersound process 18h step (1) obtained, ultrasonic power is 3000W, obtains the suspension liquid 2 of black;
(3) suspension liquid 2 step (2) obtained is pulverized and is peeled off 11h in eddy current type crusher, and the power of eddy current type crusher is 6000W, obtains the suspension liquid 3 of black;
(4) the suspension liquid 3 supersound process 18h in ice-water bath step (3) obtained, ultrasonic power is 2400W, obtains the suspension liquid 4 of black;
(5) suspension liquid 4 that step (4) obtains is transferred in the centrifuge tube of 300mL, with the centrifugal 50min of the rotating speed of 11000 revs/min, reclaimed by supernatant liquid, the stripping for next batch micro crystal graphite uses, collect lower sediment, be precipitated 1;
(6) precipitation 1 that step (5) obtains is added in the anhydrous methanol of 2500mL, the homogeneous suspension liquid 5-1 obtained after ultrasonic disperse, is transferred in the centrifuge tube of 300mL, with the centrifugal 20min of the rotating speed of 11000 revs/min, supernatant liquid is reclaimed, collects lower sediment; Repeat described operation more once, the lower sediment of collecting by this step adds in the anhydrous methanol of 2500mL, the homogeneous suspension liquid 5-2 obtained after ultrasonic disperse, be transferred in the centrifuge tube of 300mL, with the centrifugal 20min of the rotating speed of 11000 revs/min, supernatant liquid is reclaimed, collects lower sediment, be precipitated 2;
(7) precipitation 2 that step (6) obtains is added in the distilled water of 2500mL, after ultrasonic disperse, obtain homogeneous suspension liquid 6-1, be transferred in the centrifuge tube of 300mL, with the centrifugal 25min of the rotating speed of 9000 revs/min, outwell supernatant liquid, collect lower sediment; Repeat described operation more once, the lower sediment of collecting by this step adds in the distilled water of 2500mL, homogeneous suspension liquid 6-2 is obtained after ultrasonic disperse, be transferred in the centrifuge tube of 300mL, with the centrifugal 25min of the rotating speed of 9000 revs/min, outwell supernatant liquid, collect lower sediment, be precipitated 3;
(8) precipitation 3 that step (7) obtains is added in the distilled water of 150mL, homogeneous suspension liquid 7 is obtained after ultrasonic disperse 30min, ultrasonic power is 800W, suspension liquid 7 is frozen into solid in liquid nitrogen, then room temperature in vacuo is dry, vacuum tightness is 8 ~ 12MPa, obtains final product.
The final product obtained is detected as follows:
(1) X-ray powder diffraction test: as shown in Figure 1, can see the characteristic peak 25 ° of micro crystal graphite alkene, illustrate that micro crystal graphite is transformed to micro crystal graphite alkene, final product is micro crystal graphite alkene to result;
(2) x-ray photoelectron power spectrum test: result shows that the element ratio of C/O in final product is 9.7, illustrates that the Graphene oxygen level in final product is few;
(3) Raman spectrum test: result display is respectively at about 1350cm
-1and 1590cm
-1there is the D band of Graphene and the characteristic peak of E band in place, D peak represents SP
3the vibration absorption peak of the one-tenth key model of hydridization carbon, as: " C-C ", " C-O ", " C=O ", " O-C=O ", the area ratio of E band and D band is 11.2, illustrates that the defect of final product is little;
(4) microscopic examination: from scanning electronic microscope and transmission electron microscope result, the structure of final product is laminar structured, size is not in tens nanometers to hundreds of nanometer etc., be the Electron Microscopy Results of 0.2nm, selected area electron diffraction figure result and atomic force microscope test result in conjunction with resolving power, the sheet number of plies of known final product all≤7 layers.
Embodiment 10
Prepared a method for Graphene by micro crystal graphite batch, described method steps is as follows:
(1) 0.5g micro crystal graphite powder, 0.05g cetyl trimethylammonium bromide are mixed with solvent 1 magnetic agitation 2h in beaker of 5000mL, obtain the suspension liquid 1 of black, wherein, the concentration of micro crystal graphite is 0.1mg mL
-1; Described solvent 1 is mixed with volume ratio 2:1 by N-Methyl pyrrolidone and orthodichlorobenzene;
(2) suspension liquid 1 supersound process 17h step (1) obtained, ultrasonic power is 1800W, obtains the suspension liquid 2 of black;
(3) suspension liquid 2 step (2) obtained is pulverized and is peeled off 10h in eddy current type crusher, and the power of eddy current type crusher is 6000W, obtains the suspension liquid 3 of black;
(4) the suspension liquid 3 supersound process 15h in ice-water bath step (3) obtained, ultrasonic power is 2400W, obtains the suspension liquid 4 of black;
(5) suspension liquid 4 that step (4) obtains is transferred in the centrifuge tube of 300mL, with the centrifugal 10min of the rotating speed of 11000 revs/min, reclaimed by supernatant liquid, the stripping for next batch micro crystal graphite uses, collect lower sediment, be precipitated 1;
(6) precipitation 1 that step (5) obtains is added in the anhydrous isopropyl alcohol alcohol of 2500mL, the homogeneous suspension liquid 5-1 obtained after ultrasonic disperse, be transferred in the centrifuge tube of 300mL, with the centrifugal 25min of the rotating speed of 10000 revs/min, supernatant liquid is reclaimed, collects lower sediment; Repeat described operation more once, the lower sediment of collecting by this step adds in the anhydrous isopropyl alcohol of 2500mL, the homogeneous suspension liquid 5-2 obtained after ultrasonic disperse, be transferred in the centrifuge tube of 300mL, with the centrifugal 25min of the rotating speed of 10000 revs/min, supernatant liquid is reclaimed, collects lower sediment, be precipitated 2;
(7) precipitation 2 that step (6) obtains is added in the distilled water of 2500mL, after ultrasonic disperse, obtain homogeneous suspension liquid 6-1, be transferred in the centrifuge tube of 300mL, with the centrifugal 20min of the rotating speed of 8000 revs/min, outwell supernatant liquid, collect lower sediment; Repeat described operation more once, the lower sediment of collecting by this step adds in the distilled water of 2500mL, homogeneous suspension liquid 6-2 is obtained after ultrasonic disperse, be transferred in the centrifuge tube of 300mL, with the centrifugal 20min of the rotating speed of 8000 revs/min, outwell supernatant liquid, collect lower sediment, be precipitated 3;
(8) precipitation 3 that step (7) obtains is added in the distilled water of 30mL, homogeneous suspension liquid 7 is obtained after ultrasonic disperse 20min, ultrasonic power is 1200W, suspension liquid 7 is frozen into solid in liquid nitrogen, then room temperature in vacuo is dry, vacuum tightness is 8 ~ 12MPa, obtains final product.
The final product obtained is detected as follows:
(1) X-ray powder diffraction test: as shown in Figure 1, can see the characteristic peak 25 ° of micro crystal graphite alkene, illustrate that micro crystal graphite is transformed to micro crystal graphite alkene, final product is micro crystal graphite alkene to result;
(2) x-ray photoelectron power spectrum test: result shows that the element ratio of C/O in final product is 9.1, illustrates that the Graphene oxygen level in final product is few;
(3) Raman spectrum test: result display is respectively at about 1350cm
-1and 1590cm
-1there is the D band of Graphene and the characteristic peak of E band in place, D peak represents SP
3the vibration absorption peak of the one-tenth key model of hydridization carbon, as: " C-C ", " C-O ", " C=O ", " O-C=O ", the area ratio of E band and D band is 10.1, illustrates that the defect of final product is little;
(4) microscopic examination: from scanning electronic microscope and transmission electron microscope result, the structure of final product is laminar structured, size is not in tens nanometers to hundreds of nanometer etc., be the Electron Microscopy Results of 0.2nm, selected area electron diffraction figure result and atomic force microscope test result in conjunction with resolving power, the sheet number of plies of known final product all≤7 layers.
Embodiment 11
Embodiment 1 ~ 10 is obtained final product, i.e. micro crystal graphite alkene, respectively as the negative material of lithium cell after 120 DEG C of drying and processings, in glove box, be assembled into diameter is respectively 2cm button cell, be specially: using metal lithium sheet as positive electrode active materials, negative active core-shell material micro crystal graphite alkene, binding agent polyvinylidene difluoride (PVDF) (PVDF), acetylene black are mixed with the ratio of mass ratio 8:1:1, even spread lamellar on Copper Foil, disk is cut into as positive electrode material after drying, Celgard 2300 is barrier film, 1.0mol/L LiPF
6/ EC (NSC 11801)+DMC (methylcarbonate) (volume ratio of EC and DMC is 1:1) is electrolytic solution, CR2032 button cell is assembled in argon gas glove box, and adopt LAND CT2001A test macro to obtain final product to embodiment 10, namely micro crystal graphite alkene is that negative active core-shell material obtains the capacity character of button cell and recursive nature is tested, specific as follows:
Test under 0.1A/g electric current, the capacity stablizes of button cell is at 450mAh/g, and to 100 circulation times, the capacity of button cell does not also significantly reduce;
Test from multiplying power, when electric current is raised to 1000mAh/g, the capacity stablizes of button cell is at 350mAh/g, button cell is at more high current density, and as under 5A/g condition, capacity still can reach 200mAh/g, illustrate at higher current densities, button cell completes a charge and discharge process and only needs 2min, and described final product has fast charging and discharging feature, is suitable for practical application.
LAND CT2001A test macro is adopted to obtain final product to embodiment 1 ~ 9 respectively, namely micro crystal graphite alkene is that negative active core-shell material obtains the capacity character of button cell and recursive nature is tested, result with obtain final product with embodiment 10, to be namely that negative active core-shell material obtains the capacity character of button cell similar with recursive nature test result for micro crystal graphite alkene.
The present invention includes but be not limited to above embodiment, every any equivalent replacement of carrying out under the principle of spirit of the present invention or local improvement, all will be considered as within protection scope of the present invention.
Claims (7)
1. prepared a method for Graphene by micro crystal graphite batch, it is characterized in that: step is as follows:
(1) mixed by micro crystal graphite powder, tensio-active agent and solvent 1, obtain suspension liquid 1, wherein, the concentration of micro crystal graphite is 0.1mg mL
-1~ 5mg mL
-1;
Tensio-active agent is cetyl trimethylammonium bromide, sodium lauryl sulphate, sodium laurylsulfate or polyvinylpyrrolidone; Solvent 1 is the mixing solutions of organic reagent and orthodichlorobenzene, and organic reagent is N-Methyl pyrrolidone, DMF, N,N-dimethylacetamide and butyrolactone wherein one or more; Micro crystal graphite is 10:1 ~ 20:1 with the ratio of surfactant qualities;
(2) by suspension liquid 1 supersound process 5h ~ 20h, ultrasonic power is 200W ~ 3200W, obtains suspension liquid 2;
(3) by suspension liquid 2 in eddy current type crusher, pulverize peel off 5h ~ 12h, the power of eddy current type crusher is 4000W ~ 6000W, obtains suspension liquid 3;
(4) by suspension liquid 3 supersound process 5h ~ 20h in 0 DEG C ~ 5 DEG C, ultrasonic power is 200W ~ 3200W, obtains suspension liquid 4;
(5) by suspension liquid 4 centrifugation, collect lower sediment, be precipitated 1;
(6) precipitation 1 is distributed in solvent 2 forms homogeneous suspension liquid 5, centrifugation, collect lower sediment, be precipitated 2;
Described solvent 2 is dehydrated alcohol, methyl alcohol, Virahol or n-propyl alcohol;
(7) precipitation 2 is distributed in water forms homogeneous suspension liquid 6, centrifugation, collect lower sediment, be precipitated 3;
(8) precipitation 3 is distributed in water forms homogeneous suspension liquid 7, suspension liquid 7 is frozen into solid at≤10min, then vacuum-drying, obtain micro crystal graphite alkene.
2. a kind of method being prepared Graphene by micro crystal graphite batch according to claim 1, it is characterized in that: in step (1), the volume ratio of organic reagent and orthodichlorobenzene is 3:1 ~ 1:3; Adopt magnetic agitation mixing 2h ~ 12h.
3. a kind of method being prepared Graphene by micro crystal graphite batch according to claim 1, is characterized in that: in step (4), by suspension liquid 3 supersound process in ice-water bath.
4. a kind of method being prepared Graphene by micro crystal graphite batch according to claim 1, it is characterized in that: in step (5), the rotating speed of centrifugation is 8000 revs/min ~ 11000 revs/min, centrifugal 15min ~ 60min.
5. a kind of method being prepared Graphene by micro crystal graphite batch according to claim 1, is characterized in that: in step (6), carry out centrifugation after ultrasonic disperse; The rotating speed of centrifugation is 7000 revs/min ~ 11000 revs/min, centrifugal 10min ~ 30min; Step (6) carries out >=2 times.
6. a kind of method being prepared Graphene by micro crystal graphite batch according to claim 1, it is characterized in that: in step (7), the purity of water is the water of more than distilled water purity; Carry out centrifugation after ultrasonic disperse, the rotating speed of centrifugation is 7000 revs/min ~ 10000 revs/min, centrifugal 10min ~ 30min; Step (7) carries out >=2 times.
7. a kind of method being prepared Graphene by micro crystal graphite batch according to claim 1, it is characterized in that: in step (8), water is the water more than distilled water purity; Ultrasonic disperse, ultrasonic power is 200W ~ 1000W, ultrasonic 10min ~ 30min; Liquid nitrogen is adopted to carry out freezing.
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| CN107331537A (en) * | 2017-08-04 | 2017-11-07 | 太原理工大学 | A kind of preparation method and application of three-dimensional grapheme/graphite-phase nitrogen carbide |
| CN108565404A (en) * | 2017-12-23 | 2018-09-21 | 林荣铨 | It is a kind of to prepare application of the graphene/silicon carbon composite in lithium ion battery by carbon source of micro crystal graphite |
| CN108515186A (en) * | 2018-05-15 | 2018-09-11 | 中国工程物理研究院化工材料研究所 | The bismuth alkene of surfactant auxiliary, the liquid phase ultrasound stripping means of antimony alkene, black phosphorus |
| CN109160507A (en) * | 2018-10-19 | 2019-01-08 | 上海纳米技术及应用国家工程研究中心有限公司 | The magnanimity preparation method of fluorinated graphene |
| CN109133129A (en) * | 2018-11-01 | 2019-01-04 | 大连海事大学 | A kind of fractionation method of AlON transparent ceramic powder |
| CN110615430A (en) * | 2019-10-17 | 2019-12-27 | 桂林理工大学 | Novel preparation method of primary few-layer graphene |
| CN113447405A (en) * | 2020-03-26 | 2021-09-28 | 北京橡胶工业研究设计院有限公司 | Microcrystalline graphite particle size testing method |
| RU2752936C1 (en) * | 2020-12-04 | 2021-08-11 | Дмитрий Игоревич Шварцман | Method for producing graphene |
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