CN104843679A - Method for solvothermal peeling preparation of microcrystalline graphene from microcrystalline graphite - Google Patents
Method for solvothermal peeling preparation of microcrystalline graphene from microcrystalline graphite Download PDFInfo
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Abstract
The invention relates to a method for solvothermal peeling preparation of microcrystalline 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 mixed solution of o-dichlorobenzene and one or more of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethyl acetamide and butanolide to the microcrystalline graphite concentration of 1-30mg.mL<-1>; adding the obtained solution into a closed container, heating to 180-210DEG C, and stirring for 24h or more; carrying out continuous ultrasonic treatment at 0-5DEG C under 80-100W for 10min or above; centrifuging, and collecting the obtained precipitate; dispersing the precipitate in methanol or ethanol or isopropanol or n-propanol, centrifuging, and collecting the obtained new precipitate; dispersing the new precipitate in water, centrifuging, and collecting the finally obtained precipitate; and dispersing the finally obtained precipitate, freezing within 10min to form a solid, and carrying out vacuum drying to obtain the microcrystalline graphene. The method has the advantages of low cost, high grade and large reserve of the above raw material, simple preparation, low cost, and realization of amplified production.
Description
Technical field
The present invention relates to a kind of method being prepared micro crystal graphite alkene by the stripping of micro crystal graphite solvent thermal, belong to grapheme material preparing technical field.
Background technology
Graphene, is a kind of individual layer sheet structure be made up of carbon atom, is interconnected to hexagonal gridding between carbon atom.It is 2630m that Graphene has theoretical value
2g
-1bigger serface, 200000cm
2v
-1s
-1high electron mobility, excellent light transmission and physical strength, make Graphene at electron device (as: field-effect transistor, transparency electrode, solar cell etc.), energy storage device (as: ultracapacitor, lithium ion battery etc.), the fields such as Energy conversion device (as storage hydrogen, photoelectric conversion, fuel cell etc.) are widely applied, and cause the extensive concern of global scientific research personnel.
Matter of utmost importance in the investigation and application of Graphene is exactly the preparation of Graphene.Originally, Graphene is obtained from highly oriented pyrolytic graphite by mechanically peel method, but the amount of Graphene that described method obtains is considerably less, is difficult to the object reaching some scientific research and practical application.At present, the method preparing Graphene mainly comprises: epitaxial growth method, electrochemical process, organic synthesis method, chemical Vapor deposition process and oxidation reduction process etc.Wherein, oxidation reduction process can realize batch preparation, is most widely used, but defect on oxidation reduction process gained graphene sheet layer is more, and cause Graphene partial properties to decline or lose, and preparation process complexity is loaded down with trivial details, the cycle is long; Need in chemical oxidation and intercalation process to use a large amount of strong acid and oxygenant, pay higher cost, the oxynitride produced in reacted spent acid solution and reaction process, can cause environmental pollution.Except oxidation reduction process, other method output preparing Graphene are less, are only applicable to fundamental research among a small circle, are difficult to the needs meeting actual production.Up to now, also do not have the excellent process that really can be applicable to suitability for industrialized production, this has become the application of restriction Graphene, hinders the significant obstacle that it develops.
At present, the method for redox volume production Graphene, all with natural phaneritric crystalline flake graphite for raw material, China's high-quality crystalline flake graphite overexploitation in recent years.Of high grade, the reserves of China's micro crystal graphite ore are large, but the method preparing Graphene by micro crystal graphite rarely has report, and science research input is comparatively short of.
Summary of the invention
For the defect existed in prior art, the object of the present invention is to provide a kind of method being prepared micro crystal graphite alkene by the stripping of micro crystal graphite solvent thermal, described method preparation process is simple, with low cost, can amplify production.
Object of the present invention is realized by following technical scheme.
Peeled off the method preparing micro crystal graphite alkene by micro crystal graphite solvent thermal, described method steps is as follows:
(1) mixed with solvent 1 by micro crystal graphite powder, obtain the suspension liquid 1 of black, wherein, the concentration of micro crystal graphite is 1mg mL
-1~ 30mg mL
-1;
Wherein, described solvent 1 is the mixing solutions of organic reagent and orthodichlorobenzene, and described organic reagent is more than one in N-Methyl pyrrolidone, DMF, N,N-dimethylacetamide and butyrolactone; The volume ratio of preferred organic reagent and orthodichlorobenzene is 4:1 ~ 1:3; Described mixing is preferably first stirred, then ultrasonic disperse, and described ultrasonic power is preferably 80W ~ 100W;
(2) suspension liquid 1 that step (1) obtains is loaded in encloses container, be heated to 180 DEG C ~ 210 DEG C and keep described temperature, stirring reaction >=24h terminates, in described reaction process, organic agent molecule in described solvent 1 carries out uniform intercalation, stripping to graphite, obtains the suspension liquid 2 of black;
Wherein, described encloses container should prevent the corrosion of described suspension liquid 1, and tetrafluoroethylene can be selected as the reactor of liner; Stir by adding magneton in described encloses container, realize by magnetic agitation, the diameter proportion of preferred encloses container basal diameter and magneton is 2:1 ~ 5:1; Heating can adopt baking oven to realize; Preferred stirring reaction 24h ~ 72h;
(3) after the suspension liquid 2 that step (2) obtains being cooled to room temperature, in 0 DEG C ~ 5 DEG C, carry out supersound process, ultrasonic power is 80W ~ 100W, continues >=10min, obtains the suspension liquid 3 of black;
After suspension liquid 2 is cooled to room temperature, supersound process can be carried out in ice-water bath; Preferred supersound process is carried out several times, continues 10min ~ 30min at every turn;
(4) suspension liquid 3 centrifugation step (3) obtained, collects lower sediment, is precipitated 1;
The rotating speed of preferred described centrifugation is 5000 revs/min ~ 8000 revs/min, centrifugal 10min ~ 30min;
(5) precipitation 1 that step (4) obtains is distributed in solvent 2 forms homogeneous suspension liquid 4, centrifugation, collect lower sediment, be precipitated 2;
Described solvent 2 is methyl alcohol, ethanol, Virahol or n-propyl alcohol; Preferably to carry out centrifugation after the power ultrasonic of 100W ~ 500W dispersion 30min ~ 60min; The rotating speed of preferred described centrifugation is 5000 revs/min ~ 8000 revs/min, centrifugal 10min ~ 30min; Preferred steps (5) carries out >=2 times;
(6) precipitation 2 that step (5) obtains is distributed in water forms homogeneous suspension liquid 5, centrifugation, collect lower sediment, be precipitated 3;
The purity of preferably water is the water of more than distilled water purity; Preferably to carry out centrifugation after the power ultrasonic of 100W ~ 500W dispersion 30min ~ 60min; The rotating speed of preferred described centrifugation is 4000 revs/min ~ 8000 revs/min, centrifugal 10min ~ 30min; Preferred steps (6) carries out >=2 times;
(7) precipitation 3 that step (6) obtains is distributed in water forms homogeneous suspension liquid 6, suspension liquid 6 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 80W ~ 100W, ultrasonic 5min ~ 10min; Preferred employing liquid nitrogen carries out freezing.
Beneficial effect
1. the invention provides a kind of stripping by micro crystal graphite solvent thermal and prepare the method for micro crystal graphite alkene, described method is simple, easy and reliable, meanwhile, green non-pollution, productive rate is high, and required equipment is simple, can scale operation;
2. the invention provides a kind of stripping by micro crystal graphite solvent thermal and prepare the method for micro crystal graphite alkene, described method starting material micro crystal graphite cost used is low, of high grade, and China's margin is enriched; The chemical reagent used in process can be recycled, as recyclable in the supernatant liquid after centrifugation in step (4), as the stripping of solvent 1 for next batch micro crystal graphite, supernatant liquid in step (5) after centrifugation is recyclable, uses as the solvent 2 in step (5);
3. the invention provides a kind of method being prepared micro crystal graphite alkene by the stripping of micro crystal graphite solvent thermal, the number of plies of the micro crystal graphite alkene that described method obtains, below 7 layers, is minority layer graphene, be expected to be used as super light material, support of the catalyst, micro-nano electron device, and energy storage and matrix material;
4. the invention provides a kind of method being prepared micro crystal graphite alkene by the stripping of micro crystal graphite solvent thermal, the wafer of the micro crystal graphite that described method uses is less than crystalline flake graphite, produce Graphene with micro crystal graphite and not only will significantly reduce the cost of Graphene, also will make up the demand of market to small size, graphene with high specific surface simultaneously; The graphene preparation method cycle in prior art that solves is long, is difficult to the shortcoming meeting suitability for industrialized production, can utilizes the advantage of the micro crystal graphite resource of China's abundant simultaneously;
5. the invention provides a kind of method being prepared micro crystal graphite alkene by the stripping of micro crystal graphite solvent thermal, in described method steps (3), temperature is 0 DEG C ~ 5 DEG C, can prevent temperature too high make micro crystal graphite alkene reunite or again stacking, step (5) object is to wash away solvent 1 residual in suspension liquid 4, and step (6) object is to wash away solvent 2 residual in suspension liquid 5.
Accompanying drawing explanation
Fig. 1 is the photo of the black suspension 1 that in embodiment 1, step (1) obtains.
Fig. 2 is the X-ray powder diffraction test result figure of the final product obtained in embodiment 1.
Fig. 3 is the scanning electron microscope diagram of the final product obtained in embodiment 1.
Fig. 4 is the transmission electron microscope figure of the final product obtained in embodiment 1.
Fig. 5 is the resolving power of the final product obtained in embodiment 1 is 0.2nm transmission electron microscope figure.
Embodiment
Below in conjunction with the drawings and specific embodiments in detail the present invention is described in detail, but is not limited thereto.
In following examples, described baking oven is the BAO-50 type convection oven purchased from Shi Doukai plant and instrument company limited.
Embodiment 1
Peeled off the method preparing micro crystal graphite alkene by micro crystal graphite solvent thermal, described method steps is as follows:
(1) 35mg micro crystal graphite powder is taken, add in 35mL solvent 1, described solvent 1 is mixed with volume ratio 1:1 by N-Methyl pyrrolidone and orthodichlorobenzene, stirs 30min, then supersound process 30min, ultrasonic power is 80W, micro crystal graphite is mixed with solvent 1, obtains the suspension liquid 1 of black, as shown in Figure 1, wherein, the concentration of micro crystal graphite is 1mg mL
-1;
(2) suspension liquid 1 that step (1) obtains being loaded 50mL basal diameter is in the reactor of 5cm, the inner lining material of described reactor is tetrafluoroethylene, the magneton that diameter is 2.5cm is put in reactor, reactor is airtight, be heated to 180 DEG C in an oven and keep described temperature, stirring reaction 24h, obtains the suspension liquid 2 of black;
(3) after the suspension liquid 2 that in question response still, step (2) obtains is cooled to room temperature, be transferred in beaker, carry out supersound process 3 times in ice-water bath, each ultrasonic power is 90W, continues 10min, obtains the suspension liquid 3 of black;
(4) suspension liquid 3 that step (3) obtains is transferred in the centrifuge tube of 15mL, carries out centrifugation with the rotating speed of 5000 revs/min, centrifugal 10min, supernatant liquid is reclaimed, collect lower sediment, be precipitated 1;
(5) precipitation 1 that step (4) obtains is distributed in the dehydrated alcohol of 50mL, be after 100W ultrasonic disperse 60min through ultrasonic power, be transferred in the centrifuge tube of 50mL, centrifugation is carried out with the rotating speed of 5000 revs/min, after centrifugal 10min, supernatant liquid is reclaimed, collects lower sediment; Repeat described operation more once, the lower sediment of collecting by this step is distributed in the dehydrated alcohol of 50mL, be after 100W ultrasonic disperse 60min through ultrasonic power, be transferred in the centrifuge tube of 50mL, carry out centrifugation with the rotating speed of 5000 revs/min, after centrifugal 10min, supernatant liquid is reclaimed, collect lower sediment, be precipitated 2;
(6) precipitation 2 that step (5) obtains is distributed in the distilled water of 50mL, be after 100W ultrasonic disperse 60min through ultrasonic power, be transferred in the centrifuge tube of 15mL, centrifugation is carried out with the rotating speed of 4000 revs/min, after centrifugal 10min, outwell supernatant liquid, collect lower sediment; Repeat described operation more once, the lower sediment of collecting by this step is distributed in the distilled water of 50mL, be after 100W ultrasonic disperse 60min through ultrasonic power, be transferred in the centrifuge tube of 15mL, carry out centrifugation with the rotating speed of 4000 revs/min, after centrifugal 10min, outwell supernatant liquid, collect lower sediment, be precipitated 3;
(7) add in the distilled water of 5mL by the precipitation 3 that step (6) obtains, ultrasonic disperse 5min, ultrasonic power is 80W, be precipitated the aqueous solution of 3, the aqueous solution of precipitation 3 is freezing in liquid nitrogen, then carry out vacuum-drying, vacuum tightness is 8 ~ 12MPa, obtains final product.
Final product is tested as follows:
(1) X-ray powder diffraction test: result as shown in Figure 2, has occurred the characteristic diffraction peak 25 that graphene sheet layer is stacking in visible Fig. 2
o, illustrate that final product is micro crystal graphite alkene;
(2) Raman spectrum test: from the D peak intensity of the known final product of test result and the ratio (I of G peak intensity
d/ I
g); D peak represents SP
3the vibration absorption peak of the one-tenth key model of hydridization carbon, as: " C-C ", " C-O ", " C=O " etc., G peak represents SP
2the vibration absorption peak of the one-tenth key model of hydridization carbon, i.e.: " C=C ", I
d/ I
gvalue be that 0.11, G peak intensity is comparatively large, the structure not destruction of final product is described; Show that final product defect is less by Raman test result, quality is higher;
(3) Electron microscopy: as shown in Figure 3, as shown in Figure 4, the final product that can see is the laminated structure that tens nanometer arrives several microns to transmission electron microscope detected result to scanning electronic microscope detected result; It is that 0.2nm transmission electron microscope detects that (a) point on Stochastic choice final product and (b) point carry out resolving power, result as shown in Figure 5, the lamella that visible final product (a) is put is 7 layers, and the lamella that final product (b) is put is 3 layers.
Embodiment 2
Peeled off the method preparing micro crystal graphite alkene by micro crystal graphite solvent thermal, described method steps is as follows:
(1) 9g micro crystal graphite powder is taken, add in 1500mL solvent 1, described solvent 1 is mixed with volume ratio 1:3 by DMF and orthodichlorobenzene, stirs 30min, then supersound process 30min, ultrasonic power is 100W, and micro crystal graphite is mixed with solvent 1, obtains the suspension liquid 1 of black, wherein, the concentration of micro crystal graphite is 6mg mL
-1;
(2) suspension liquid 1 that step (1) obtains being loaded 2000mL basal diameter is in the reactor of 15cm, the inner lining material of described reactor is tetrafluoroethylene, the magneton that diameter is 3cm is put in reactor, reactor is airtight, be heated to 210 DEG C in an oven and keep described temperature, stirring reaction 72h, obtains the suspension liquid 2 of black;
(3) after the suspension liquid 2 that in question response still, step (2) obtains is cooled to room temperature, be transferred in beaker, carry out supersound process 3 times in ice-water bath, each ultrasonic power is 100W, continues 30min, obtains black suspension 3;
(4) suspension liquid 3 that step (3) obtains is transferred in the centrifuge tube of 300mL, carries out centrifugation with the rotating speed of 8000 revs/min, centrifugal 10min, supernatant liquid is reclaimed, collect lower sediment, be precipitated 1;
(5) precipitation 1 that step (4) obtains is distributed in the anhydrous methanol of 1000mL, be after 500W ultrasonic disperse 30min through ultrasonic power, be transferred in the centrifuge tube of 300mL, centrifugation is carried out with the rotating speed of 6000 revs/min, after centrifugal 20min, supernatant liquid is reclaimed, collects lower sediment; Repeat described operation more once, the lower sediment of collecting by this step is distributed in the anhydrous methanol of 1000mL, be after 500W ultrasonic disperse 30min through ultrasonic power, be transferred in the centrifuge tube of 300mL, carry out centrifugation with the rotating speed of 6000 revs/min, after centrifugal 20min, supernatant liquid is reclaimed, collect lower sediment, be precipitated 2;
(6) precipitation 2 that step (5) obtains is distributed in the distilled water of 1000mL, be after 500W ultrasonic disperse 30min through ultrasonic power, be transferred in the centrifuge tube of 300mL, centrifugation is carried out with the rotating speed of 5000 revs/min, after centrifugal 20min, outwell supernatant liquid, collect lower sediment; Repeat described operation more once, the lower sediment of collecting by this step is distributed in the distilled water of 1000mL, be after 500W ultrasonic disperse 30min through ultrasonic power, be transferred in the centrifuge tube of 300mL, carry out centrifugation with the rotating speed of 5000 revs/min, after centrifugal 20min, outwell supernatant liquid, collect lower sediment, be precipitated 3;
(7) add in the distilled water of 20mL by the precipitation 3 that step (6) obtains, ultrasonic disperse 10min, ultrasonic power is 100W, be precipitated the aqueous solution of 3, the aqueous solution of precipitation 3 is freezing in liquid nitrogen, then carry out vacuum-drying, vacuum tightness is 8 ~ 12MPa, obtains final product.
Final product is tested as follows:
(1) X-ray powder diffraction test: the characteristic diffraction peak 25 that graphene sheet layer is stacking has appearred in result
o, illustrate that final product is micro crystal graphite alkene;
(2) Raman spectrum test: the D peak intensity of final product and the ratio (I of G peak intensity as can be known from the results
d/ I
g); D peak represents SP
3the vibration absorption peak of the one-tenth key model of hydridization carbon, as: " C-C ", " C-O ", " C=O " etc., G peak represents SP
2the vibration absorption peak of the one-tenth key model of hydridization carbon, i.e.: " C=C ", I
d/ I
gvalue be that 0.13, G peak intensity is comparatively large, the structure not destruction of final product is described; Show that final product defect is less by Raman test result, quality is higher;
(3) Electron microscopy: from scanning electronic microscope detected result and transmission electron microscope detected result, the final product that can see is the laminated structure that tens nanometer arrives several microns; It is that 0.2nm transmission electron microscope detects that (a) point on Stochastic choice final product and (b) point carry out resolving power, and the lamella of result display final product is below 7 layers.
Embodiment 3
Peeled off the method preparing micro crystal graphite alkene by micro crystal graphite solvent thermal, described method steps is as follows:
(1) 22.5g micro crystal graphite powder is taken, add in 750mL solvent 1, described solvent 1 is mixed with volume ratio 1:2 by N,N-dimethylacetamide and orthodichlorobenzene, stirs 30min, then supersound process 30min, ultrasonic power is 100W, and micro crystal graphite is mixed with solvent 1, obtains the suspension liquid 1 of black, wherein, the concentration of micro crystal graphite is 30mg mL
-1;
(2) suspension liquid 1 that step (1) obtains being loaded 1000mL basal diameter is in the reactor of 10cm, the inner lining material of described reactor is tetrafluoroethylene, the magneton that diameter is 2.5cm is put in reactor, reactor is airtight, be heated to 210 DEG C in an oven and keep described temperature, stirring reaction 72h, obtains the suspension liquid 2 of black;
(3) after the suspension liquid 2 that in question response still, step (2) obtains is cooled to room temperature, be transferred in beaker, carry out supersound process 3 times in ice-water bath, each ultrasonic power is 100W, continues 20min, obtains the suspension liquid 3 of black;
(4) suspension liquid 3 that step (3) obtains is transferred in the centrifuge tube of 300mL, carries out centrifugation with the rotating speed of 7000 revs/min, centrifugal 30min, supernatant liquid is reclaimed, collect lower sediment, be precipitated 1;
(5) precipitation 1 that step (4) obtains is distributed in the anhydrous n-propyl alcohol of 1000mL, be after 200W ultrasonic disperse 50min through ultrasonic power, be transferred in the centrifuge tube of 300mL, centrifugation is carried out with the rotating speed of 6000 revs/min, after centrifugal 30min, supernatant liquid is reclaimed, collects lower sediment; Repeat described operation more once, by this step collect lower sediment be distributed to 1000mL without in n-propyl alcohol, be after 200W ultrasonic disperse 50min through ultrasonic power, be transferred in the centrifuge tube of 300mL, carry out centrifugation with the rotating speed of 6000 revs/min, after centrifugal 30min, supernatant liquid is reclaimed, collect lower sediment, be precipitated 2;
(6) precipitation 2 that step (5) obtains is distributed in the distilled water of 1000mL, be after 200W ultrasonic disperse 50min through ultrasonic power, be transferred in the centrifuge tube of 300mL, centrifugation is carried out with the rotating speed of 5000 revs/min, after centrifugal 30min, outwell supernatant liquid, collect lower sediment; Repeat described operation more once, the lower sediment of collecting by this step is distributed in the distilled water of 1000mL, be after 200W ultrasonic disperse 50min through ultrasonic power, be transferred in the centrifuge tube of 300mL, carry out centrifugation with the rotating speed of 5000 revs/min, after centrifugal 30min, outwell supernatant liquid, collect lower sediment, be precipitated 3;
(7) precipitation 3 that step (6) obtains is added in the distilled water of 100mL, ultrasonic disperse 10min.Ultrasonic power is 100W, is precipitated the aqueous solution of 3, and the aqueous solution of precipitation 3 is freezing in liquid nitrogen, then carries out vacuum-drying, and vacuum tightness is 8 ~ 12MPa, obtains final product.
Final product is tested as follows:
(1) X-ray powder diffraction test: the characteristic diffraction peak 25 that graphene sheet layer is stacking has appearred in result
o, illustrate that final product is micro crystal graphite alkene;
(2) Raman spectrum test: the D peak intensity of final product and the ratio (I of G peak intensity as can be known from the results
d/ I
g); D peak represents SP
3the vibration absorption peak of the one-tenth key model of hydridization carbon, as: " C-C ", " C-O ", " C=O " etc., G peak represents SP
2the vibration absorption peak of the one-tenth key model of hydridization carbon, i.e.: " C=C ", I
d/ I
gvalue be that 0.13, G peak intensity is comparatively large, the structure not destruction of final product is described; Show that final product defect is less by Raman test result, quality is higher;
(3) Electron microscopy: from scanning electronic microscope detected result and transmission electron microscope detected result, the final product that can see is the laminated structure that tens nanometer arrives several microns; (a) point on Stochastic choice final product and (b) point carry out the transmission electron microscope detection that resolving power is 0.2nm, and the lamella of result display final product is below 7 layers.
Embodiment 4
Peeled off the method preparing micro crystal graphite alkene by micro crystal graphite solvent thermal, described method steps is as follows:
(1) 11g micro crystal graphite powder is taken, add in 750mL solvent 1, described solvent 1 is mixed with volume ratio 1:1:1 by N,N-dimethylacetamide, N-Methyl pyrrolidone and orthodichlorobenzene, stirs 30min, then supersound process 30min, ultrasonic power is 100W, and micro crystal graphite is mixed with solvent 1, obtains the suspension liquid 1 of black, wherein, the concentration of micro crystal graphite is 15mg mL
-1;
(2) suspension liquid 1 that step (1) obtains being loaded 1000mL basal diameter is in the reactor of 15cm, the inner lining material of described reactor is tetrafluoroethylene, the magneton that diameter is 3cm is put in reactor, reactor is airtight, be heated to 200 DEG C in an oven and keep described temperature, stirring reaction 60h, obtains the suspension liquid 2 of black;
(3) after the suspension liquid 2 that in question response still, step (2) obtains is cooled to room temperature, be transferred in beaker, carry out supersound process 3 times in ice-water bath, each ultrasonic power is 90W, continues 15min, obtains the suspension liquid 3 of black;
(4) suspension liquid 3 that step (3) obtains is transferred in the centrifuge tube of 100mL, carries out centrifugation with the rotating speed of 6000 revs/min, centrifugal 20min, supernatant liquid is reclaimed, collect lower sediment, be precipitated 1;
(5) precipitation 1 that step (4) obtains is distributed in the anhydrous isopropyl alcohol of 800mL, be after 300W ultrasonic disperse 45min through ultrasonic power, be transferred in the centrifuge tube of 100mL, centrifugation is carried out with the rotating speed of 5000 revs/min, after centrifugal 30min, supernatant liquid is reclaimed, collects lower sediment; Repeat described operation more once, the lower sediment of collecting by this step is distributed in the anhydrous isopropyl alcohol of 800mL, be after 300W ultrasonic disperse 45min through ultrasonic power, be transferred in the centrifuge tube of 100mL, carry out centrifugation with the rotating speed of 5000 revs/min, after centrifugal 30min, supernatant liquid is reclaimed, collect lower sediment, be precipitated 2;
(6) precipitation 2 that step (5) obtains is distributed in the distilled water of 1000mL, be after 300W ultrasonic disperse 45min through ultrasonic power, be transferred in the centrifuge tube of 100mL, centrifugation is carried out with the rotating speed of 5000 revs/min, after centrifugal 30min, outwell supernatant liquid, collect lower sediment; Repeat described operation more once, the lower sediment of collecting by this step is distributed in the distilled water of 1000mL, be after 300W ultrasonic disperse 45min through ultrasonic power, be transferred in the centrifuge tube of 100mL, carry out centrifugation with the rotating speed of 5000 revs/min, after centrifugal 30min, outwell supernatant liquid, collect lower sediment, be precipitated 3;
(7) add in the distilled water of 50mL by the precipitation 3 that step (6) obtains, ultrasonic disperse 8min, ultrasonic power is 90W, be precipitated the aqueous solution of 3, the aqueous solution of precipitation 3 is freezing in liquid nitrogen, then carry out vacuum-drying, vacuum tightness is 8 ~ 12MPa, obtains final product.
Final product is tested as follows:
(1) X-ray powder diffraction test: the characteristic diffraction peak 25 that graphene sheet layer is stacking has appearred in result
o, illustrate that final product is micro crystal graphite alkene;
(2) Raman spectrum test: the D peak intensity of final product and the ratio (I of G peak intensity as can be known from the results
d/ I
g); D peak represents SP
3the vibration absorption peak of the one-tenth key model of hydridization carbon, as: " C-C ", " C-O ", " C=O " etc., G peak represents SP
2the vibration absorption peak of the one-tenth key model of hydridization carbon, i.e.: " C=C ", I
d/ I
gvalue be that 0.12, G peak intensity is comparatively large, the structure not destruction of final product is described; Show that final product defect is less by Raman test result, quality is higher;
(3) Electron microscopy: from scanning electronic microscope detected result and transmission electron microscope detected result, the final product that can see is the laminated structure that tens nanometer arrives several microns; (a) point on Stochastic choice final product and (b) point carry out the transmission electron microscope detection that resolving power is 0.2nm, and the lamella of result display final product is below 7 layers.
Embodiment 5
Peeled off the method preparing micro crystal graphite alkene by micro crystal graphite solvent thermal, described method steps is as follows:
(1) 4.5g micro crystal graphite powder is taken, add in 450mL solvent 1, described solvent 1 is mixed with volume ratio 3:1 by butyrolactone and orthodichlorobenzene, stir 30min, then supersound process 30min, ultrasonic power is 90W, micro crystal graphite is mixed with solvent 1, obtain the suspension liquid 1 of black, wherein, the concentration of micro crystal graphite is 10mg mL
-1;
(2) suspension liquid 1 that step (1) obtains being loaded 500mL basal diameter is in the reactor of 6cm, the inner lining material of described reactor is tetrafluoroethylene, put into the magneton that diameter is 3cm, reactor is airtight, be heated to 200 DEG C in an oven and keep described temperature, stirring reaction 36h, obtains the suspension liquid 2 of black;
(3) after the suspension liquid 2 that in question response still, step (2) obtains is cooled to room temperature, be transferred in beaker, carry out supersound process 3 times in ice-water bath, each ultrasonic power is 80W, continues 15min, obtains the suspension liquid 3 of black;
(4) suspension liquid 3 that step (3) obtains is transferred in the centrifuge tube of 100mL, carries out centrifugation with the rotating speed of 7500 revs/min, centrifugal 15min, supernatant liquid is reclaimed, collect lower sediment, be precipitated 1;
(5) precipitation 1 that step (4) obtains is distributed in the dehydrated alcohol of 500mL, be after 400W ultrasonic disperse 40min through ultrasonic power, be transferred in the centrifuge tube of 100mL, centrifugation is carried out with the rotating speed of 7000 revs/min, after centrifugal 15min, supernatant liquid is reclaimed, collects lower sediment; Repeat described operation more once, the lower sediment of collecting by this step is distributed in the dehydrated alcohol of 500mL, be after 400W ultrasonic disperse 40min through ultrasonic power, be transferred in the centrifuge tube of 100mL, carry out centrifugation with the rotating speed of 7000 revs/min, after centrifugal 15min, supernatant liquid is reclaimed, collect lower sediment, be precipitated 2;
(6) precipitation 2 that step (5) obtains is distributed in the distilled water of 500mL, be after 400W ultrasonic disperse 40min through ultrasonic power, be transferred in the centrifuge tube of 100mL, centrifugation is carried out with the rotating speed of 6000 revs/min, after centrifugal 15min, outwell supernatant liquid, collect lower sediment; Repeat described operation more once, the lower sediment of collecting by this step is distributed in the distilled water of 500mL, be after 400W ultrasonic disperse 40min through ultrasonic power, be transferred in the centrifuge tube of 100mL, carry out centrifugation with the rotating speed of 6000 revs/min, after centrifugal 15min, outwell supernatant liquid, collect lower sediment, be precipitated 3;
(7) add in the distilled water of 50mL by the precipitation 3 that step (6) obtains, ultrasonic disperse 7min, ultrasonic power is 90W, be precipitated the aqueous solution of 3, the aqueous solution of precipitation 3 is freezing in liquid nitrogen, then carry out vacuum-drying, vacuum tightness is 8 ~ 12Mpa, obtains final product.
Final product is tested as follows:
(1) X-ray powder diffraction test: the characteristic diffraction peak 25 that graphene sheet layer is stacking has appearred in result
o, illustrate that final product is micro crystal graphite alkene;
(2) Raman spectrum test: the D peak intensity of final product and the ratio (I of G peak intensity as can be known from the results
d/ I
g); D peak represents SP
3the vibration absorption peak of the one-tenth key model of hydridization carbon, as: " C-C ", " C-O ", " C=O " etc., G peak represents SP
2the vibration absorption peak of the one-tenth key model of hydridization carbon, i.e.: " C=C ", I
d/ I
gvalue be that 0.10, G peak intensity is comparatively large, the structure not destruction of final product is described; Raman test result shows that final product defect is less, and quality is higher;
(3) Electron microscopy: from scanning electronic microscope detected result and transmission electron microscope detected result, the final product that can see is the laminated structure that tens nanometer arrives several microns; (a) point on Stochastic choice final product and (b) point carry out the transmission electron microscope detection that resolving power is 0.2nm, and the lamella of result display final product is below 7 layers.
Embodiment 6
Peeled off the method preparing micro crystal graphite alkene by micro crystal graphite solvent thermal, described method steps is as follows:
(1) 0.15g micro crystal graphite powder is taken, add in 75mL solvent 1, described solvent 1 is mixed with volume ratio 0.5:0.5:1 by N-Methyl pyrrolidone, butyrolactone and orthodichlorobenzene, stir 30min, then supersound process 30min, ultrasonic power is 80W, micro crystal graphite is mixed with solvent 1, obtain the suspension liquid 1 of black, wherein, the concentration of micro crystal graphite is 2mg mL
-1;
(2) suspension liquid 1 that step (1) obtains being loaded 100mL basal diameter is in the reactor of 6cm, the inner lining material of described reactor is tetrafluoroethylene, the magneton that diameter is 2cm is put in reactor, reactor is airtight, be heated to 190 DEG C in an oven and keep described temperature, stirring reaction 24h, obtains the suspension liquid 2 of black;
(3) after the suspension liquid 2 that in question response still, step (2) obtains is cooled to room temperature, be transferred in beaker, carry out supersound process 3 times in ice-water bath, each ultrasonic power is 80W, continues 15min, obtains the suspension liquid 3 of black;
(4) suspension liquid 3 that step (3) obtains is transferred in the centrifuge tube of 20mL, carries out centrifugation with the rotating speed of 5000 revs/min, centrifugal 15min, supernatant liquid is reclaimed, collect lower sediment, be precipitated 1;
(5) precipitation 1 that step (4) obtains is distributed in the anhydrous isopropyl alcohol of 100mL, be after 250W ultrasonic disperse 60min through ultrasonic power, be transferred in the centrifuge tube of 20mL, centrifugation is carried out with the rotating speed of 6000 revs/min, after centrifugal 20min, supernatant liquid is reclaimed, collects lower sediment; Repeat described operation more once, the lower sediment of collecting by this step is distributed in the anhydrous isopropyl alcohol of 100mL, be after 250W ultrasonic disperse 60min through ultrasonic power, be transferred in the centrifuge tube of 20mL, carry out centrifugation with the rotating speed of 6000 revs/min, after centrifugal 20min, supernatant liquid is reclaimed, collect lower sediment, be precipitated 2;
(6) precipitation 2 that step (5) obtains is distributed in the distilled water of 100mL, be after 250W ultrasonic disperse 60min through ultrasonic power, be transferred in the centrifuge tube of 20mL, centrifugation is carried out with the rotating speed of 5000 revs/min, after centrifugal 20min, outwell supernatant liquid, collect lower sediment; Repeat described operation more once, the lower sediment of collecting by this step is distributed in the distilled water of 100mL, be after 250W ultrasonic disperse 60min through ultrasonic power, be transferred in the centrifuge tube of 20mL, carry out centrifugation with the rotating speed of 5000 revs/min, after centrifugal 20min, outwell supernatant liquid, collect lower sediment, be precipitated 3;
(7) add in the distilled water of 10mL by the precipitation 3 that step (6) obtains, ultrasonic disperse 9min, ultrasonic power is 80W, be precipitated the aqueous solution of 3, the aqueous solution of precipitation 3 is freezing in liquid nitrogen, then carry out vacuum-drying, vacuum tightness is 8 ~ 12MPa, obtains final product.
Final product is tested as follows:
(1) X-ray powder diffraction test: the characteristic diffraction peak 25 that graphene sheet layer is stacking has appearred in result
o, illustrate that final product is micro crystal graphite alkene;
(2) Raman spectrum test: the D peak intensity of final product and the ratio (I of G peak intensity as can be known from the results
d/ I
g); D peak represents SP
3the vibration absorption peak of the one-tenth key model of hydridization carbon, as: " C-C ", " C-O ", " C=O " etc., G peak represents SP
2the vibration absorption peak of the one-tenth key model of hydridization carbon, i.e.: " C=C ", I
d/ I
gvalue be that 0.09, G peak intensity is comparatively large, the structure not destruction of final product is described; Show that final product defect is less by Raman test result, quality is higher;
(3) Electron microscopy: from scanning electronic microscope detected result and transmission electron microscope detected result, the final product that can see is the laminated structure that tens nanometer arrives several microns; (a) point on Stochastic choice final product and (b) point carry out the transmission electron microscope detection that resolving power is 0.2nm, and the lamella of result display final product is below 7 layers.
Embodiment 7
Peeled off the method preparing micro crystal graphite alkene by micro crystal graphite solvent thermal, described method steps is as follows:
(1) 30g micro crystal graphite powder is taken, add in 1500mL solvent 1, described solvent 1 is mixed with volume ratio 1.5:1.5:1 by N-Methyl pyrrolidone, DMF and orthodichlorobenzene, stirs 30min, then supersound process 30min, ultrasonic power is 100W, and micro crystal graphite is mixed with solvent 1, obtains the suspension liquid 1 of black, wherein, the concentration of micro crystal graphite is 20mg mL
-1;
(2) suspension liquid 1 that step (1) obtains being loaded 2000mL basal diameter is in the reactor of 15cm, the inner lining material of described reactor is tetrafluoroethylene, the magneton that diameter is 6cm is put in reactor, reactor is airtight, be heated to 200 DEG C in an oven and keep described temperature, stirring reaction 24h, obtains the suspension liquid 2 of black;
(3) after the suspension liquid 2 that in question response still, step (2) obtains is cooled to room temperature, be transferred in beaker, carry out supersound process 3 times in ice-water bath, each ultrasonic power is 80W, continues 30min, obtains the suspension liquid 3 of black;
(4) suspension liquid 3 that step (3) obtains is transferred in the centrifuge tube of 200mL, carries out centrifugation with the rotating speed of 5000 revs/min, centrifugal 10min, supernatant liquid is reclaimed, collect lower sediment, be precipitated 1;
(5) precipitation 1 that step (4) obtains is distributed in the dehydrated alcohol of 800mL, be after 500W ultrasonic disperse 50min through ultrasonic power, be transferred in the centrifuge tube of 100mL, centrifugation is carried out with the rotating speed of 8000 revs/min, after centrifugal 30min, supernatant liquid is reclaimed, collects lower sediment; Repeat described operation more once, the lower sediment of collecting by this step is distributed in the dehydrated alcohol of 800mL, be after 500W ultrasonic disperse 50min through ultrasonic power, be transferred in the centrifuge tube of 100mL, carry out centrifugation with the rotating speed of 8000 revs/min, after centrifugal 30min, supernatant liquid is reclaimed, collect lower sediment, be precipitated 2;
(6) precipitation 2 that step (5) obtains is distributed in the distilled water of 900mL, be after 500W ultrasonic disperse 50min through ultrasonic power, be transferred in the centrifuge tube of 100mL, centrifugation is carried out with the rotating speed of 4000 revs/min, after centrifugal 30min, outwell supernatant liquid, collect lower sediment; Repeat described operation more once, the lower sediment of collecting by this step is distributed in the distilled water of 900mL, be after 500W ultrasonic disperse 50min through ultrasonic power, be transferred in the centrifuge tube of 100mL, carry out centrifugation with the rotating speed of 4000 revs/min, after centrifugal 30min, outwell supernatant liquid, collect lower sediment, be precipitated 3;
(7) add in the distilled water of 20mL by the precipitation 3 that step (6) obtains, ultrasonic disperse 5min, ultrasonic power is 80W, be precipitated the aqueous solution of 3, the aqueous solution of precipitation 3 is freezing in liquid nitrogen, then carry out vacuum-drying, vacuum tightness is 8 ~ 12MPa, obtains final product.
Final product is tested as follows:
(1) X-ray powder diffraction test: the characteristic diffraction peak 25 that graphene sheet layer is stacking has appearred in result
o, illustrate that final product is micro crystal graphite alkene;
(2) Raman spectrum test: the D peak intensity of final product and the ratio (I of G peak intensity as can be known from the results
d/ I
g); D peak represents SP
3the vibration absorption peak of the one-tenth key model of hydridization carbon, as: " C-C ", " C-O ", " C=O " etc., G peak represents SP
2the vibration absorption peak of the one-tenth key model of hydridization carbon, i.e.: " C=C ", I
d/ I
gvalue be that 0.12, G peak intensity is comparatively large, the structure not destruction of final product is described; Show that final product defect is less by Raman test result, quality is higher;
(3) Electron microscopy: from scanning electronic microscope detected result and transmission electron microscope detected result, the final product that can see is the laminated structure that tens nanometer arrives several microns; (a) point on Stochastic choice final product and (b) point carry out the transmission electron microscope detection that resolving power is 0.2nm, and the lamella of result display final product is below 7 layers.
Embodiment 8
Peeled off the method preparing micro crystal graphite alkene by micro crystal graphite solvent thermal, described method steps is as follows:
(1) 25g micro crystal graphite powder is taken, add in 1500mL solvent 1, described solvent 1 is mixed with volume ratio 1:1:1:1 by N-Methyl pyrrolidone, N,N-dimethylacetamide, butyrolactone and orthodichlorobenzene, stirs 30min, then supersound process 30min, ultrasonic power is 100W, and micro crystal graphite is mixed with solvent 1, obtains the suspension liquid 1 of black, wherein, the concentration of micro crystal graphite is 17mg mL
-1;
(2) suspension liquid 1 that step (1) obtains being loaded 2000mL basal diameter is in the reactor of 15cm, the inner lining material of described reactor is tetrafluoroethylene, the magneton that diameter is 4cm is put in reactor, reactor is airtight, be heated to 180 DEG C in an oven and keep described temperature, stirring reaction 70h, obtains the suspension liquid 2 of black;
(3) after the suspension liquid 2 that in question response still, step (2) obtains is cooled to room temperature, be transferred in beaker, carry out supersound process 3 times in ice-water bath, each ultrasonic power is 90W, continues 30min, obtains the suspension liquid 3 of black;
(4) suspension liquid 3 that step (3) obtains is transferred in the centrifuge tube of 100mL, carries out centrifugation with the rotating speed of 6000 revs/min, centrifugal 30min, supernatant liquid is reclaimed, collect lower sediment, be precipitated 1;
(5) precipitation 1 that step (4) obtains is distributed in the dehydrated alcohol of 900mL, be after 200W ultrasonic disperse 50min through ultrasonic power, be transferred in the centrifuge tube of 100mL, centrifugation is carried out with the rotating speed of 6000 revs/min, after centrifugal 30min, supernatant liquid is reclaimed, collects lower sediment; Repeat described operation more once, the lower sediment of collecting by this step is distributed in the dehydrated alcohol of 900mL, be after 200W ultrasonic disperse 50min through ultrasonic power, be transferred in the centrifuge tube of 100mL, carry out centrifugation with the rotating speed of 6000 revs/min, after centrifugal 30min, supernatant liquid is reclaimed, collect lower sediment, be precipitated 2;
(6) precipitation 2 that step (5) obtains is distributed in the distilled water of 700mL, be after 400W ultrasonic disperse 40min through ultrasonic power, be transferred in the centrifuge tube of 100mL, centrifugation is carried out with the rotating speed of 5000 revs/min, after centrifugal 20min, outwell supernatant liquid, collect lower sediment; Repeat described operation more once, the lower sediment of collecting by this step is distributed in the distilled water of 700mL, be after 400W ultrasonic disperse 40min through ultrasonic power, be transferred in the centrifuge tube of 100mL, carry out centrifugation with the rotating speed of 5000 revs/min, after centrifugal 20min, outwell supernatant liquid, collect lower sediment, be precipitated 3;
(7) add in the distilled water of 60mL by the precipitation 3 that step (6) obtains, ultrasonic disperse 8min, ultrasonic power is 90W, be precipitated the aqueous solution of 3, the aqueous solution of precipitation 3 is freezing in liquid nitrogen, then carry out vacuum-drying, vacuum tightness is 8 ~ 12MPa, obtains final product.
Final product is tested as follows:
(1) X-ray powder diffraction test: the characteristic diffraction peak 25 that graphene sheet layer is stacking has appearred in result
o, illustrate that final product is micro crystal graphite alkene;
(2) Raman spectrum test: the D peak intensity of final product and the ratio (I of G peak intensity as can be known from the results
d/ I
g); D peak represents SP
3the vibration absorption peak of the one-tenth key model of hydridization carbon, as: " C-C ", " C-O ", " C=O " etc., G peak represents SP
2the vibration absorption peak of the one-tenth key model of hydridization carbon, i.e.: " C=C ", I
d/ I
gvalue be that 0.14, G peak intensity is comparatively large, the structure not destruction of final product is described; Show that final product defect is less by Raman test result, quality is higher;
(3) Electron microscopy: from scanning electronic microscope detected result and transmission electron microscope detected result, the final product that can see is the laminated structure that tens nanometer arrives several microns; (a) point on Stochastic choice final product and (b) point carry out the transmission electron microscope detection that resolving power is 0.2nm, and the lamella of result display final product is below 7 layers.
Embodiment 9
Peeled off the method preparing micro crystal graphite alkene by micro crystal graphite solvent thermal, described method steps is as follows:
(1) 3.6g micro crystal graphite powder is taken, add in 900mL solvent 1, described solvent 1 is by N-Methyl pyrrolidone, N,N-dimethylacetamide, N, dinethylformamide, butyrolactone and orthodichlorobenzene mix with volume ratio 1:1:1:1:1, stir 30min, then supersound process 30min, ultrasonic power is 100W, micro crystal graphite is mixed with solvent 1, obtain the suspension liquid 1 of black, wherein, the concentration of micro crystal graphite is 4mg mL
-1;
(2) suspension liquid 1 that step (1) obtains being loaded 1200mL basal diameter is in the reactor of 12cm, the inner lining material of described reactor is tetrafluoroethylene, the magneton that diameter is 4cm is put in reactor, reactor is airtight, be heated to 200 DEG C in an oven and keep described temperature, stirring reaction 65h, obtains the suspension liquid 2 of black;
(3) after the suspension liquid 2 that in question response still, step (2) obtains is cooled to room temperature, be transferred in beaker, carry out supersound process 3 times in ice-water bath, each ultrasonic power is 90W, continues 10min, obtains black suspension 3;
(4) suspension liquid 3 that step (3) obtains is transferred in the centrifuge tube of 50mL, carries out centrifugation with the rotating speed of 8000 revs/min, centrifugal 30min, supernatant liquid is reclaimed, collect lower sediment, be precipitated 1;
(5) precipitation 1 that step (4) obtains is distributed in the anhydrous isopropyl alcohol of 500mL, be after 500W ultrasonic disperse 30min through ultrasonic power, be transferred in the centrifuge tube of 100mL, centrifugation is carried out with the rotating speed of 8000 revs/min, after centrifugal 20min, supernatant liquid is reclaimed, collects lower sediment; Repeat described operation more once, the lower sediment of collecting by this step is distributed in the anhydrous isopropyl alcohol of 500mL, be after 500W ultrasonic disperse 30min through ultrasonic power, be transferred in the centrifuge tube of 100mL, carry out centrifugation with the rotating speed of 8000 revs/min, after centrifugal 20min, supernatant liquid is reclaimed, collect lower sediment, be precipitated 2;
(6) precipitation 2 that step (5) obtains is distributed in the distilled water of 500mL, is after 200W ultrasonic disperse 60min through ultrasonic power, is transferred in the centrifuge tube of 100mL, centrifugal with the rotating speed of 7000 revs/min, after centrifugal 10min, outwell supernatant liquid, collect lower sediment; Repeat described operation more once, the lower sediment of collecting by this step is distributed in the distilled water of 500mL, be after 200W ultrasonic disperse 60min through ultrasonic power, be transferred in the centrifuge tube of 100mL, carry out centrifugation with the rotating speed of 7000 revs/min, after centrifugal 10min, outwell supernatant liquid, collect lower sediment, be precipitated 3;
(7) add in the distilled water of 20mL by the precipitation 3 that step (6) obtains, ultrasonic disperse 7min, ultrasonic power is 100W, be precipitated the aqueous solution of 3, the aqueous solution of precipitation 3 is freezing in liquid nitrogen, then carry out vacuum-drying, vacuum tightness is 8 ~ 12MPa, obtains final product.
Final product is tested as follows:
(1) X-ray powder diffraction test: the characteristic diffraction peak 25 that graphene sheet layer is stacking has appearred in result
o, illustrate that final product is micro crystal graphite alkene;
(2) Raman spectrum test: the D peak intensity of final product and the ratio (I of G peak intensity as can be known from the results
d/ I
g); D peak represents SP
3the vibration absorption peak of the one-tenth key model of hydridization carbon, as: " C-C ", " C-O ", " C=O " etc., G peak represents SP
2the vibration absorption peak of the one-tenth key model of hydridization carbon, i.e.: " C=C ", I
d/ I
gvalue be that 0.11, G peak intensity is comparatively large, the structure not destruction of final product is described; Show that final product defect is less by Raman test result, quality is higher;
(3) Electron microscopy: from scanning electronic microscope detected result and transmission electron microscope detected result, the final product that can see is the laminated structure that tens nanometer arrives several microns; (a) point on Stochastic choice final product and (b) point carry out the transmission electron microscope detection that resolving power is 0.2nm, and the lamella of result display final product is below 7 layers.
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 (8)
1. peeled off the method preparing micro crystal graphite alkene by micro crystal graphite solvent thermal, it is characterized in that: step is as follows:
(1) mixed with solvent 1 by micro crystal graphite powder, obtain suspension liquid 1, the concentration of micro crystal graphite is 1mg mL
-1~ 30mg mL
-1;
Solvent 1 is the mixing solutions of organic reagent and orthodichlorobenzene, and organic reagent is more than one in N-Methyl pyrrolidone, DMF, N,N-dimethylacetamide and butyrolactone;
(2) load in encloses container by suspension liquid 1, be heated to 180 DEG C ~ 210 DEG C and keep described temperature, stirring reaction >=24h terminates, and obtains suspension liquid 2;
(3) after suspension liquid 2 being cooled to room temperature, in 0 DEG C ~ 5 DEG C, carry out supersound process, ultrasonic power is 80W ~ 100W, continues >=10min, obtains suspension liquid 3;
(4) by suspension liquid 3 centrifugation, collect lower sediment, be precipitated 1;
(5) precipitation 1 is distributed in solvent 2 forms homogeneous suspension liquid 4, centrifugation, collect lower sediment, be precipitated 2;
Described solvent 2 is methyl alcohol, ethanol, Virahol or n-propyl alcohol;
(6) precipitation 2 is distributed in water forms homogeneous suspension liquid 5, centrifugation, collect lower sediment, be precipitated 3;
(7) precipitation 3 is distributed in water forms homogeneous suspension liquid 6, suspension liquid 6 is frozen into solid at≤10min, then carries out vacuum-drying, obtains micro crystal graphite alkene.
2. a kind of method being prepared micro crystal graphite alkene by the stripping of micro crystal graphite solvent thermal according to claim 1, it is characterized in that: in step (1), the volume ratio of organic reagent and orthodichlorobenzene is 4:1 ~ 1:3; Be mixed into and first stir, then ultrasonic disperse; Ultrasonic power is 80W ~ 100W.
3. a kind of method being prepared micro crystal graphite alkene by the stripping of micro crystal graphite solvent thermal according to claim 1, is characterized in that: in step (2), and encloses container is with the reactor of tetrafluoroethylene as liner; In encloses container, add magneton carry out magnetic agitation; The diameter proportion of encloses container basal diameter and magneton is 2:1 ~ 5:1; Stirring reaction 24h ~ 72h.
4. a kind of method being prepared micro crystal graphite alkene by the stripping of micro crystal graphite solvent thermal according to claim 1, is characterized in that: in step (3), after suspension liquid 2 is cooled to room temperature, in ice-water bath, carry out supersound process; Supersound process is carried out several times, continues 10min ~ 30min at every turn.
5. a kind of method being prepared micro crystal graphite alkene by the stripping of micro crystal graphite solvent thermal according to claim 1, it is characterized in that: in step (4), the rotating speed of centrifugation is 5000 revs/min ~ 8000 revs/min, centrifugal 10min ~ 30min.
6. a kind of method being prepared micro crystal graphite alkene by the stripping of micro crystal graphite solvent thermal according to claim 1, is characterized in that: in step (5), to carry out centrifugation after the power ultrasonic of 100W ~ 500W dispersion 30min ~ 60min; The rotating speed of centrifugation is 5000 revs/min ~ 8000 revs/min, centrifugal 10min ~ 30min; Step (5) carries out >=2 times.
7. a kind of method being prepared micro crystal graphite alkene by the stripping of micro crystal graphite solvent thermal according to claim 1, it is characterized in that: in step (6), the purity of water is the water of more than distilled water purity; To carry out centrifugation after the power ultrasonic of 100W ~ 500W dispersion 30min ~ 60min; The rotating speed of described centrifugation is 4000 revs/min ~ 8000 revs/min, centrifugal 10min ~ 30min; Step (6) carries out >=2 times.
8. a kind of method being prepared micro crystal graphite alkene by the stripping of micro crystal graphite solvent thermal according to claim 1, it is characterized in that: in step (7), water is the water more than distilled water purity; Ultrasonic disperse, ultrasonic power is 80W ~ 100W, ultrasonic 5min ~ 10min; Liquid nitrogen is adopted to carry out freezing.
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