CN104843680B - The method that graphene is prepared by micro crystal graphite batch - Google Patents
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Abstract
The present invention relates to a kind of method for preparing graphene by micro crystal graphite batch, belong to grapheme material preparing technical field.Methods described is as follows：Micro crystal graphite powder, surfactant and solvent 1 are well mixed, the concentration of micro crystal graphite is 0.1~5mg mL‑1；Ultrasonically treated 5~20h, ultrasonic power is 200~3200W；In power in 4000~6000W eddy current type crusher, 5~12h is peeled off in crushing；Ultrasonically treated 5~20h in 0~5 DEG C, ultrasonic power is 200~3200W；Centrifuge, collect precipitation；It is distributed in solvent 2, centrifuges, collects precipitation；It is distributed in water, centrifuges, collects precipitation；It is distributed in water, solid is frozen into≤10min, is dried in vacuo, obtains micro crystal graphite alkene.Methods described is simple, reliable, and raw material micro crystal graphite cost used is low, storage level abundant and is adapted to batch production.
Description
Technical field
The present invention relates to a kind of method for preparing graphene by micro crystal graphite batch, specifically, be related to it is a kind of with stone
In solvent and the mixed solution of surfactant that black alkene surface can be approached, peel off micro crystal graphite to prepare the side of micro crystal graphite alkene
Method, methods described is ultrasound and crushes stripping method, belongs to grapheme material preparing technical field.
Background technology
Graphene is most thin, most hard nano material, its conductive good, high mechanical strength, ratio in the world at present
Surface area is big, bent, translucency is good and the advantages of high chemically stable, can be used in ultralight flak jackets, ultra-thin and ultra-light type aircraft
Material, protective coating, microelectronic is (such as：The substitute of silicon may be turned into, ultra micro transistor npn npn is manufactured, for producing not
The supercomputer come, the higher electron mobility of carbon can make the computer in future obtain higher speed) and it is new
Energy field is (such as：Ultracapacitor, lithium ion battery) in terms of.
The method for preparing graphene at present is very more, mainly includes machine synthetic method, chemical vapour deposition technique, epitaxial growth
Method, organic synthesis method and oxidation-reduction method etc..Wherein, the preparation process complexity of organic synthesis method is cumbersome, and the cycle is long, it is difficult to advise
Modelling is produced；Chemical vapour deposition technique is more ripe, and continuous production can be achieved, but product subsequent transfer would generally be dirty by substrate
Dye；The graphene film that epitaxial growth method is obtained is uniform, but needs hot conditions, and pattern is difficult to control to；Mechanical stripping method
Although simple, yield is extremely low, it is impossible to meet the requirement of industrialized production；Oxidation-reduction method can largely prepare graphene,
It is the method for preparing graphene the most frequently used at present, still, oxidation-reduction method is related to chemical oxidation and intercalation process, can cause stone
Defect on black alkene lamella is more, causes the performance for having a strong impact on graphene, such as electric conductivity, thermal conductivity, chemical stability etc.,
So as to influence the application of graphene.It would therefore be highly desirable to develop method that is a kind of easy and effective and high-quality graphene being prepared in batches.
It is crystalline flake graphite to prepare graphene method in batches at present raw materials used, and China's micro crystal graphite reserves are up to 2,000,000,000
Ton, is micro crystal graphite producing country maximum in the world, but the R and D to micro crystal graphite are extremely limited, generally with raw material
Outlet.With the exhaustive exploitation of China's high-quality graphite, research and development micro crystal graphite is extremely urgent.
The content of the invention
The defect existed for prior art, graphite is prepared it is an object of the invention to provide one kind by micro crystal graphite batch
The method of alkene, specifically, be related to it is a kind of in the solvent and surfactant that can be approached with graphenic surface, by micro crystal graphite
By excusing from death, the method that stripping prepares micro crystal graphite alkene is crushed, methods described can utilize the micro crystal graphite resource of China's abundant, system
Standby process is simple, with low cost, can be mass-produced.
The purpose of the present invention is realized by following technical scheme.
A kind of method for preparing graphene by micro crystal graphite batch, methods described step is as follows：
(1) micro crystal graphite powder, surfactant and solvent 1 are well mixed, obtain the suspension 1 of black, wherein, it is micro-
The concentration of spar ink is 0.1mg mL-1~5mg mL-1；
Wherein, surfactant is cetyl trimethylammonium bromide, lauryl sodium sulfate, sldium lauryl sulfate or poly-
Vinylpyrrolidone；Solvent 1 is the mixed solution of organic reagent and o-dichlorohenzene, and the organic reagent is N- crassitudes
Ketone, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide and butyrolactone one or more therein；It is preferred that organic reagent
Volume ratio with o-dichlorohenzene is 3:1~1:3；It is preferred that mixing 2h~12h, mixing can use magnetic agitation；Micro crystal graphite and table
Face activating agent mass ratio is 10:1~20:1；
(2) the ultrasonically treated 5h~20h of suspension 1 for obtaining step (1), ultrasonic power is 200W~3200W, obtains black
The suspension 2 of color；
(3) suspension 2 for obtaining step (2) crush in eddy current type crusher and peels off 5h~12h, the whirlpool
The power of streaming crusher is 4000W~6000W, obtains the suspension 3 of black, wherein containing less than 7 layers of micro crystal graphite alkene；
(4) suspension 3 for obtaining step (3) ultrasonically treated 5h~20h in 0 DEG C~5 DEG C, ultrasonic power be 200W~
3200W, obtains the suspension 4 of black；
It can be carried out in ice-water bath ultrasonically treated；
(5) suspension 4 for obtaining step (4) is centrifuged, and is collected lower sediment, is obtained precipitation 1；
It is preferred that the rotating speed of the centrifugation is 8000 revs/min~11000 revs/min, 15min~60min is centrifuged；
(6) precipitation 1 for obtaining step (5), which is distributed in solvent 2, forms homogeneous suspension 5, centrifuges, and collects lower floor
Precipitation, obtains precipitation 2；
The solvent 2 is absolute ethyl alcohol, methanol, isopropanol or normal propyl alcohol；
It is preferred that being centrifuged after ultrasonic disperse；It is preferred that the rotating speed of the centrifugation is 7000 revs/min~11000
Rev/min, centrifuge 10min~30min；Preferred steps (6) are carried out >=2 times；
(7) precipitation 2 for obtaining step (6), which is distributed in water, forms homogeneous suspension 6, centrifuges, and collects lower floor and sinks
Form sediment, obtain precipitation 3；
It is preferred that the purity of water is water more than distilled water purity；It is preferred that being centrifuged after ultrasonic disperse；It is preferred that described
The rotating speed of centrifugation is 7000 revs/min~10000 revs/min, centrifuges 10min~30min；Preferred steps (7) carry out >=2
It is secondary；
(8) precipitation 3 for obtaining step (7), which is distributed in water, forms homogeneous suspension 7, and suspension 7 is cold in≤10min
Solid is frozen into, then is dried in vacuo, micro crystal graphite alkene is obtained；
It is preferred that water is the water more than distilled water purity；It is preferred that ultrasonic disperse, ultrasonic power is 200W~1000W, ultrasound
10min~30min；It is preferred to use liquid nitrogen to be freezed.
Beneficial effect
1. the invention provides a kind of method for preparing graphene by micro crystal graphite batch, methods described is simple, reliable, institute
Raw material micro crystal graphite cost is low, storage level abundant and is adapted to batch production；
2. the invention provides a kind of method for preparing graphene by micro crystal graphite batch, methods described is made with micro crystal graphite
For raw material raw material prepare micro crystal graphite alkene, with the market crystalline flake graphite prepare graphene do not possess small size, surface
The characteristics of product is greatly and electronic conductivity is high, can develop the energy storage and transition material of good properties, can be used as super
The electrode material of capacitor, lithium ion battery, fuel-cell catalyst and senior electrically conductive ink etc.；
3. the invention provides a kind of method for preparing graphene by micro crystal graphite batch, microlite prepared by methods described
Black alkene can be used to improve the multifunctionality of composite and processing characteristics of composite etc., prepare unique physics, chemistry and
The composite of mechanical performance, broader practice field is provided for composite, realizes the multifunction application of graphene；
4. the invention provides a kind of method for preparing graphene by micro crystal graphite batch, in methods described：Step (2)
Purpose is micro crystal graphite being partially stripped, and forms micro crystal graphite relatively thin compared with raw material micro crystal graphite；Step (3)
Purpose is further to peel off the micro crystal graphite relatively thin compared with raw material that step (2) is obtained into less than 7 layers of micro crystal graphite
Alkene；It is ultrasonically treated in 0 DEG C~5 DEG C in step (4), prevent temperature is too high from micro crystal graphite alkene is reunited or is stacked again, step
(4) purpose is step (3) further peeling off into micro crystal graphite alkene without complete micro crystal graphite is peeled off；In step (5)
Supernatant liquor is reclaimed as solvent 1, so that the stripping of next group micro crystal graphite is used；Step (6), which reclaims supernatant liquor, to be made
Used for solvent 2, the purpose of step (6) is to wash away the solvent 1 remained in micro crystal graphite alkene；The purpose of step (7) is to wash
Remove the solvent 2 remained in micro crystal graphite alkene.
Brief description of the drawings
Fig. 1 is the X-ray powder diffraction test result figure of the final product obtained in embodiment 1.
Fig. 2 is the SEM testing result figure of the final product obtained in embodiment 1.
Fig. 3 is the transmission electron microscope testing result figure of the final product obtained in embodiment 1.
Fig. 4 be the final product obtained in embodiment 1 resolution ratio be 0.2nm transmission electron microscope testing result
Figure.
Fig. 5 is the SEAD figure of the final product obtained in embodiment 1.
Embodiment
To be best understood from the present invention, the present invention is described in further detail with reference to specific embodiment, but is not limited to
This.
The producer of eddy current type crusher described in following examples is：Xian Chang ultrasonic equipments Co., Ltd, model：
XC-CD-1800。
Embodiment 1
A kind of method for preparing graphene by micro crystal graphite batch, methods described step is as follows：
(1) by 0.1g micro crystal graphites powder, 0.01g cetyl trimethylammonium bromides and 1000mL solvent 1 in beaker
Middle magnetic agitation 2h is well mixed, and obtains the suspension 1 of black, wherein, the concentration of micro crystal graphite is 0.1mg mL-1；It is described molten
Agent 1 is by 1-METHYLPYRROLIDONE and o-dichlorohenzene with volume ratio 1:1 mixes；
(2) the ultrasonically treated 5h of suspension 1 for obtaining step (1), ultrasonic power is 200W, obtains the suspension 2 of black；
(3) suspension 2 for obtaining step (2) crushes stripping 5h, the work(of eddy current type crusher in eddy current type crusher
Rate is 4000W, obtains the suspension 3 of black；
(4) suspension 3 for obtaining step (3) ultrasonically treated 5h in ice-water bath, ultrasonic power is 200W, obtains black
Suspension 4；
(5) suspension 4 for obtaining step (4) is transferred in 50mL centrifuge tube, with 11000 revs/min of rotating speed from
Heart 15min, supernatant liquor is reclaimed, so that the stripping of next group micro crystal graphite is used, and is collected lower sediment, is obtained precipitation 1；
(6) precipitation 1 for obtaining step (5) is added in 500mL absolute ethyl alcohol, and what is obtained after ultrasonic disperse is homogeneous
Suspension 5-1, is transferred in 50mL centrifuge tube, centrifuges 20min with 7000 revs/min of rotating speed, supernatant liquor is reclaimed, and receives
Collect lower sediment；Repeat it is described operation once, will this step collect lower sediment add 500mL absolute ethyl alcohol in, pass through
The homogeneous suspension 5-2 obtained after ultrasonic disperse, is transferred in 50mL centrifuge tube, is centrifuged with 7000 revs/min of rotating speed
20min, supernatant liquor is reclaimed, and is collected lower sediment, is obtained precipitation 2；
(7) precipitation 2 obtained step (6) is added in 500mL distilled water, obtains homogeneous suspended after ultrasonic disperse
Liquid 6-1, is transferred in 50mL centrifuge tube, and 30min is centrifuged with 7000 revs/min of rotating speed, outwells supernatant liquor, collects lower floor
Precipitation；Repeat it is described operation once, will this step collect lower sediment addition 500mL distilled water in, through ultrasonic disperse
Homogeneous suspension 6-2 is obtained afterwards, is transferred in 50mL centrifuge tube, and 30min is centrifuged with 7000 revs/min of rotating speed, outwelled
Supernatant liquor, collects lower sediment, obtains precipitation 3；
(8) precipitation 3 for obtaining step (7) is added in 10mL distilled water, obtains homogeneous after ultrasonic disperse 10min
Suspension 7, ultrasonic power is 200W, and suspension 7 is frozen into solid in liquid nitrogen, and then room temperature in vacuo is dried, and vacuum is 8
~12MPa, obtains final product.
Obtained final product is detected as follows：
(1) X-ray powder diffraction is tested：As a result it is as shown in Figure 1, it can be seen that 25 ° of the characteristic peak of micro crystal graphite alkene, explanation
Micro crystal graphite is transformed to micro crystal graphite alkene, and final product is micro crystal graphite alkene；
(2) x-ray photoelectron power spectrum is tested：As a result the element ratio for showing C/O in final product is 9.7, illustrates final production
Graphene oxygen content in thing is few；
(3) Raman spectrum is tested：As a result show respectively in about 1350cm-1And 1590cm-1Place occurs in that the D of graphene
The characteristic peak of band and E bands, D peaks represent SP3The vibration absorption peak of the bonding model of hydridization carbon, such as：" C-C ", " C-O ", " C=O ",
The area ratio of " O-C=O ", E bands and D bands is 10.5, illustrates that the defect of final product is seldom；
(4) microscope is detected：SEM result is as shown in Fig. 2 transmission electron microscope result such as Fig. 3 institutes
Show, from Fig. 2,3, the structure of final product be it is laminar structured, size at tens nanometers to hundreds of nanometers, with reference to point
Resolution is 0.2nm Electron Microscopy Results as shown in figure 4, SEAD figure result is as shown in figure 5, and atom
Force microscope test chart, it is known that the piece number of plies of final product is respectively 2,4 and 7 layers ,≤7 layers.
Embodiment 2
A kind of method for preparing graphene by micro crystal graphite batch, methods described step is as follows：
(1) by 12g micro crystal graphites powder, 0.6g lauryl sodium sulfate and 5000mL solvent 1, magnetic force is stirred in beaker
Mix 6h to be well mixed, obtain the suspension 1 of black, wherein, the concentration of micro crystal graphite is 2.4mgmL-1；The solvent 1 is by N, N-
Dimethylformamide and o-dichlorohenzene are with volume ratio 1:3 mix；
(2) the ultrasonically treated 12h of suspension 1 for obtaining step (1), ultrasonic power is 2000W, obtains the suspension of black
2；
(3) suspension 2 for obtaining step (2) crushes stripping 8h, the work(of eddy current type crusher in eddy current type crusher
Rate is 5000W, obtains the suspension 3 of black；
(4) suspension 3 for obtaining step (3) ultrasonically treated 12h in ice-water bath, ultrasonic power is 2000W, obtains black
The suspension 4 of color；
(5) suspension 4 for obtaining step (4) is transferred in 300mL centrifuge tube, with 9000 revs/min of rotating speed from
Heart 40min, supernatant liquor is reclaimed, so that the stripping of next group micro crystal graphite is used, and is collected lower sediment, is obtained precipitation 1；
(6) precipitation 1 for obtaining step (5) is added in 1500mL anhydrous normal propyl alcohol, and what is obtained after ultrasonic disperse is equal
One suspension 5-1, is transferred in 300mL centrifuge tube, 10min is centrifuged with 11000 revs/min of rotating speed, by supernatant liquor
Reclaim, collect lower sediment；Repeat it is described operation once, will this step collect lower sediment addition 1500mL it is anhydrous just
In propyl alcohol, the homogeneous suspension 5-2 obtained after ultrasonic disperse is transferred in 300mL centrifuge tube, with 11000 revs/min
Rotating speed centrifugation 10min, supernatant liquor is reclaimed, collect lower sediment, obtain precipitation 2；
(7) precipitation 2 for obtaining step (6) is added in 1500mL distilled water, and homogeneous hang is obtained after ultrasonic disperse
Turbid liquid 6-1, is transferred in 300mL centrifuge tube, centrifuges 30min with 9000 revs/min of rotating speed, outwells supernatant liquor, collects
Lower sediment；Repeat it is described operation once, will this step collect lower sediment addition 1500mL distilled water in, through ultrasound
Homogeneous suspension 6-2 is obtained after scattered, is transferred in 300mL centrifuge tube, 30min is centrifuged with 9000 revs/min of rotating speed,
Supernatant liquor is outwelled, lower sediment is collected, obtains precipitation 3；
(8) precipitation 3 for obtaining step (7) adds 80mL distilled water, obtains homogeneous after 20min after ultrasonic disperse
Suspension 7, ultrasonic power is 500W, and suspension 7 is frozen into solid in liquid nitrogen, and then room temperature in vacuo is dried, and vacuum is 8
~12MPa, obtains final product.
Obtained final product is detected as follows：
(1) X-ray powder diffraction is tested：As a result it is as shown in Figure 1, it can be seen that 25 ° of the characteristic peak of micro crystal graphite alkene, explanation
Micro crystal graphite is transformed to micro crystal graphite alkene, and final product is micro crystal graphite alkene；
(2) x-ray photoelectron power spectrum is tested：As a result the element ratio for showing C/O in final product is 9.9, illustrates final production
Graphene oxygen content in thing is few；
(3) Raman spectrum is tested：As a result show respectively in about 1350cm-1And 1590cm-1Place occurs in that the D of graphene
The characteristic peak of band and E bands, D peaks represent SP3The vibration absorption peak of the bonding model of hydridization carbon, such as：" C-C ", " C-O ", " C=O ",
The area ratio of " O-C=O ", E bands and D bands is 11.5, illustrates that the defect of final product is seldom；
(4) microscope is detected：From SEM and transmission electron microscope result, the structure of final product
It is laminar structured, size is at tens nanometers to hundreds of nanometers, with reference to the Electron microscopy knot that resolution ratio is 0.2nm
Really, SEAD figure result and AFM test result, it is known that the piece number of plies of final product≤7 layers.
Embodiment 3
A kind of method for preparing graphene by micro crystal graphite batch, methods described step is as follows：
(1) by 10g micro crystal graphites powder, 1g sldium lauryl sulfates and 2000mL solvent 1 in beaker magnetic agitation 12h
It is well mixed, the suspension 1 of black is obtained, wherein, the concentration of micro crystal graphite is 5mgmL-1；The solvent 1 is by N, N- dimethyl
Acetamide and o-dichlorohenzene are with volume ratio 1:2 mix；
(2) the ultrasonically treated 20h of suspension 1 for obtaining step (1), ultrasonic power is 3200W, obtains the suspension of black
2；
(3) suspension 2 for obtaining step (2) crushes stripping 12h, the work(of eddy current type crusher in eddy current type crusher
Rate is 6000W, obtains the suspension 3 of black；
(4) suspension 3 for obtaining step (3) ultrasonically treated 20h in 0 DEG C of ice-water bath, ultrasonic power is 3200W, is obtained
To the suspension 4 of black；
(5) suspension 4 for obtaining step (4) is transferred in 300mL centrifuge tube, with 9000 revs/min of rotating speed from
Heart 60min, supernatant liquor is reclaimed, so that the stripping of next group micro crystal graphite is used, and is collected lower sediment, is obtained precipitation 1；
(6) precipitation 1 for obtaining step (5) is added in 2500mL anhydrous isopropyl alcohol, and what is obtained after ultrasonic disperse is equal
One suspension 5-1, is transferred in 300mL centrifuge tube, and 30min is centrifuged with 9000 revs/min of rotating speed, and supernatant liquor is returned
Receive, collect lower sediment；Repeat it is described operation once, will this step collect lower sediment addition 2500mL anhydrous isopropyl
In alcohol, the homogeneous suspension 5-2 obtained after ultrasonic disperse is transferred in 300mL centrifuge tube, with 9000 revs/min
Rotating speed centrifuges 30min, and supernatant liquor is reclaimed, and collects lower sediment, obtains precipitation 2；
(7) precipitation 2 for obtaining step (6) is added in 2500mL distilled water, and homogeneous hang is obtained after ultrasonic disperse
Turbid liquid 6-1, is transferred in 300mL centrifuge tube, centrifuges 10min with 10000 revs/min of rotating speed, outwells supernatant liquor, collects
Lower sediment；Repeat it is described operation once, will this step collect lower sediment addition 2500mL distilled water in, through ultrasound
Homogeneous suspension 6-2 is obtained after scattered, is transferred in 300mL centrifuge tube, is centrifuged with 10000 revs/min of rotating speed
10min, outwells supernatant liquor, collects lower sediment, obtains precipitation 3；
(8) precipitation 3 for obtaining step (7) is added in 120mL distilled water, obtains homogeneous after ultrasonic disperse 20min
Suspension 7, ultrasonic power is 800W, and suspension 7 is frozen into solid in liquid nitrogen, then room temperature in vacuo dry, vacuum
For 8~12MPa, final product is obtained.
Obtained final product is detected as follows：
(1) X-ray powder diffraction is tested：As a result it is as shown in Figure 1, it can be seen that 25 ° of the characteristic peak of micro crystal graphite alkene, explanation
Micro crystal graphite is transformed to micro crystal graphite alkene, and final product is micro crystal graphite alkene；
(2) x-ray photoelectron power spectrum is tested：As a result the element ratio for showing C/O in final product is 9.2, illustrates final production
Graphene oxygen content in thing is few；
(3) Raman spectrum is tested：As a result show respectively in about 1350cm-1And 1590cm-1Place occurs in that the D of graphene
The characteristic peak of band and E bands, D peaks represent SP3The vibration absorption peak of the bonding model of hydridization carbon, such as：" C-C ", " C-O ", " C=O ",
The area ratio of " O-C=O ", E bands and D bands is 10.9, illustrates that the defect of final product is seldom；
(4) microscope is detected：From SEM and transmission electron microscope result, the structure of final product
It is laminar structured, size is at tens nanometers to hundreds of nanometers, with reference to the Electron microscopy knot that resolution ratio is 0.2nm
Really, SEAD figure result and AFM test result, it is known that the piece number of plies of final product≤7 layers.
Embodiment 4
A kind of method for preparing graphene by micro crystal graphite batch, methods described step is as follows：
(1) by 25g micro crystal graphites powder, 1.5g cetyl trimethylammonium bromides and 5000mL solvent 1 in beaker
Magnetic agitation 2h is well mixed, and obtains the suspension 1 of black, wherein, the concentration of micro crystal graphite is 5mg mL-1；The solvent 1 by
Butyrolactone and o-dichlorohenzene are with volume ratio 3:1 mixes；
(2) the ultrasonically treated 20h of suspension 1 for obtaining step (1), ultrasonic power is 3200W, obtains the suspension of black
2；
(3) suspension 2 for obtaining step (2) crushes stripping 12h, the work(of eddy current type crusher in eddy current type crusher
Rate is 6000W, obtains the suspension 3 of black；
(4) suspension 3 for obtaining step (3) ultrasonically treated 20h in 5 DEG C of water-baths, ultrasonic power is 3200W, is obtained
The suspension 4 of black；
(5) suspension 4 for obtaining step (4) is transferred in 300mL centrifuge tube, with 11000 revs/min of rotating speed from
Heart 60min, supernatant liquor is reclaimed, so that the stripping of next group micro crystal graphite is used, and is collected lower sediment, is obtained precipitation 1；
(6) precipitation 1 for obtaining step (5) is added in 2500mL absolute methanol, and what is obtained after ultrasonic disperse is homogeneous
Suspension 5-1, be transferred in 300mL centrifuge tube, 30min centrifuged with 11000 revs/min of rotating speed, supernatant liquor is returned
Receive, collect lower sediment；Repeat it is described operation once, will this step collect lower sediment addition 2500mL absolute methanol
In, the homogeneous suspension 5-2 obtained after ultrasonic disperse is transferred in 300mL centrifuge tube, with 11000 revs/min turn
Speed centrifugation 30min, supernatant liquor is reclaimed, lower sediment is collected, obtains precipitation 2；
(7) precipitation 2 for obtaining step (6) is added in 2500mL distilled water, and homogeneous hang is obtained after ultrasonic disperse
Turbid liquid 6-1, is transferred in 300mL centrifuge tube, centrifuges 30min with 10000 revs/min of rotating speed, outwells supernatant liquor, collects
Lower sediment；Repeat it is described operation once, will this step collect lower sediment addition 2500mL distilled water in, through ultrasound
Homogeneous suspension 6-2 is obtained after scattered, is transferred in 300mL centrifuge tube, is centrifuged with 10000 revs/min of rotating speed
30min, outwells supernatant liquor, collects lower sediment, obtains precipitation 3；
(8) precipitation 3 for obtaining step (7) is added in 200mL distilled water, obtains homogeneous after ultrasonic disperse 30min
Suspension 7, ultrasonic power is 1000W, and suspension 7 is frozen into solid in liquid nitrogen, then room temperature in vacuo dry, vacuum
For 8~12MPa, final product is obtained.
Obtained final product is detected as follows：
(1) X-ray powder diffraction is tested：As a result it is as shown in Figure 1, it can be seen that 25 ° of the characteristic peak of micro crystal graphite alkene, explanation
Micro crystal graphite is transformed to micro crystal graphite alkene, and final product is micro crystal graphite alkene；
(2) x-ray photoelectron power spectrum is tested：As a result the element ratio for showing C/O in final product is 9.8, illustrates final production
Graphene oxygen content in thing is few；
(3) Raman spectrum is tested：As a result show respectively in about 1350cm-1And 1590cm-1Place occurs in that the D of graphene
The characteristic peak of band and E bands, D peaks represent SP3The vibration absorption peak of the bonding model of hydridization carbon, such as：" C-C ", " C-O ", " C=O ",
The area ratio of " O-C=O ", E bands and D bands is 11.2, illustrates that the defect of final product is seldom；
(4) microscope is detected：From SEM and transmission electron microscope result, the structure of final product
It is laminar structured, size is at tens nanometers to hundreds of nanometers, with reference to the Electron microscopy knot that resolution ratio is 0.2nm
Really, SEAD figure result and AFM test result, it is known that the piece number of plies of final product≤7 layers.
Embodiment 5
A kind of method for preparing graphene by micro crystal graphite batch, methods described step is as follows：
(1) by 9g micro crystal graphites powder, 0.9g cetyl trimethylammonium bromides and 3000mL solvent 1 in beaker magnetic
Power stirring 2h is well mixed, and obtains the suspension 1 of black, wherein, the concentration of micro crystal graphite is 3mg mL-1；The solvent 1 is by fourth
Lactone and o-dichlorohenzene are with volume ratio 2:1 mixes；
(2) the ultrasonically treated 9h of suspension 1 for obtaining step (1), ultrasonic power is 1600W, obtains the suspension of black
2；
(3) suspension 2 for obtaining step (2) crushes stripping 10h, the work(of eddy current type crusher in eddy current type crusher
Rate is 4500W, obtains the suspension 3 of black；
(4) suspension 3 for obtaining step (3) ultrasonically treated 15h in 3 DEG C of water-baths, ultrasonic power is 2500W, is obtained
The suspension 4 of black；
(5) suspension 4 for obtaining step (4) is transferred in 150mL centrifuge tube, with 8000 revs/min of rotating speed from
Heart 30min, supernatant liquor is reclaimed, so that the stripping of next group micro crystal graphite is used, and is collected lower sediment, is obtained precipitation 1；
(6) precipitation 1 for obtaining step (5) is added in 2000mL absolute ethyl alcohol, and what is obtained after ultrasonic disperse is homogeneous
Suspension 5-1, be transferred in 150mL centrifuge tube, 30min centrifuged with 9000 revs/min of rotating speed, supernatant liquor is returned
Receive, collect lower sediment；Repeat it is described operation once, will this step collect lower sediment addition 2000mL absolute ethyl alcohol
In, the homogeneous suspension 5-2 obtained after ultrasonic disperse is transferred in 150mL centrifuge tube, with 9000 revs/min turn
Speed centrifugation 30min, supernatant liquor is reclaimed, lower sediment is collected, obtains precipitation 2；
(7) precipitation 2 for obtaining step (6) is added in 2000mL distilled water, and homogeneous hang is obtained after ultrasonic disperse
Turbid liquid 6-1, is transferred in 150mL centrifuge tube, centrifuges 10min with 10000 revs/min of rotating speed, outwells supernatant liquor, collects
Lower sediment；Repeat it is described operation once, will this step collect lower sediment addition 2000mL distilled water in, through ultrasound
Homogeneous suspension 6-2 is obtained after scattered, is transferred in 150mL centrifuge tube, is centrifuged with 10000 revs/min of rotating speed
10min, outwells supernatant liquor, collects lower sediment, obtains precipitation 3；
(8) precipitation 3 for obtaining step (7) is added in 100mL distilled water, obtains homogeneous after ultrasonic disperse 30min
Suspension 7, ultrasonic power is 500W, and suspension 7 is frozen into solid in liquid nitrogen, then room temperature in vacuo dry, vacuum
For 8~12MPa, final product is obtained.
Obtained final product is detected as follows：
(1) X-ray powder diffraction is tested：As a result it is as shown in Figure 1, it can be seen that 25 ° of the characteristic peak of micro crystal graphite alkene, explanation
Micro crystal graphite is transformed to micro crystal graphite alkene, and final product is micro crystal graphite alkene；
(2) x-ray photoelectron power spectrum is tested：As a result the element ratio for showing C/O in final product is 9.3, illustrates final production
Graphene oxygen content in thing is few；
(3) Raman spectrum is tested：As a result show respectively in about 1350cm-1And 1590cm-1Place occurs in that the D of graphene
The characteristic peak of band and E bands, D peaks represent SP3The vibration absorption peak of the bonding model of hydridization carbon, such as：" C-C ", " C-O ", " C=O ",
The area ratio of " O-C=O ", E bands and D bands is 10.5, illustrates that the defect of final product is seldom；
(4) microscope is detected：From SEM and transmission electron microscope result, the structure of final product
It is laminar structured, size is at tens nanometers to hundreds of nanometers, with reference to the Electron microscopy knot that resolution ratio is 0.2nm
Really, SEAD figure result and AFM test result, it is known that the piece number of plies of final product≤7 layers.
Embodiment 6
A kind of method for preparing graphene by micro crystal graphite batch, methods described step is as follows：
(1) by 0.5g micro crystal graphites powder, 0.05g polyvinylpyrrolidones and 1000mL solvent 1 in beaker magnetic force
Stir 6h to be well mixed, obtain the suspension 1 of black, wherein, the concentration of micro crystal graphite is 0.5mg mL-1；The solvent 1 is by N-
Methyl pyrrolidone, butyrolactone and o-dichlorohenzene are successively with volume ratio 0.5:0.5:1 mixes；
(2) the ultrasonically treated 18h of suspension 1 for obtaining step (1), ultrasonic power is 2400W, obtains the suspension of black
2；
(3) suspension 2 for obtaining step (2) crushes stripping 9h, the work(of eddy current type crusher in eddy current type crusher
Rate is 5500W, obtains the suspension 3 of black,；
(4) suspension 3 for obtaining step (3) ultrasonically treated 16h in 2 DEG C of water-baths, ultrasonic power is 1200W, is obtained
The suspension 4 of black；
(5) suspension 4 for obtaining step (4) is transferred in 50mL centrifuge tube, is centrifuged with 8000 revs/min of rotating speed
25min, supernatant liquor is reclaimed, so that the stripping of next group micro crystal graphite is used, and is collected lower sediment, is obtained precipitation 1；
(6) precipitation 1 for obtaining step (5) is added in 800mL absolute ethyl alcohol, and what is obtained after ultrasonic disperse is homogeneous
Suspension 5-1, is transferred in 50mL centrifuge tube, centrifuges 15min with 8000 revs/min of rotating speed, supernatant liquor is reclaimed, and receives
Collect lower sediment；Repeat it is described operation once, will this step collect lower sediment add 800mL absolute ethyl alcohol in, pass through
The homogeneous suspension 5-2 obtained after ultrasonic disperse, is transferred in 50mL centrifuge tube, is centrifuged with 8000 revs/min of rotating speed
15min, supernatant liquor is reclaimed, and is collected lower sediment, is obtained precipitation 2；
(7) precipitation 2 obtained step (6) is added in 800mL distilled water, obtains homogeneous suspended after ultrasonic disperse
Liquid 6-1, is transferred in 50mL centrifuge tube, centrifuges 10min with 10000 revs/min of rotating speed, supernatant liquor is outwelled, under collection
Layer precipitation；Repeat it is described operation once, will this step collect lower sediment add 800mL distilled water in, through ultrasound divide
Homogeneous suspension 6-2 is obtained after dissipating, is transferred in 50mL centrifuge tube, 10min is centrifuged with 10000 revs/min of rotating speed, is fallen
Fall supernatant liquor, collect lower sediment, obtain precipitation 3；
(8) precipitation 3 for obtaining step (7) is added in 70mL distilled water, obtains homogeneous after ultrasonic disperse 12min
Suspension 7, ultrasonic power is 900W, and suspension 7 is frozen into solid in liquid nitrogen, and then room temperature in vacuo is dried, and vacuum is 8
~12MPa, obtains final product.
Obtained final product is detected as follows：
(1) X-ray powder diffraction is tested：As a result it is as shown in Figure 1, it can be seen that 25 ° of the characteristic peak of micro crystal graphite alkene, explanation
Micro crystal graphite is transformed to micro crystal graphite alkene, and final product is micro crystal graphite alkene；
(2) x-ray photoelectron power spectrum is tested：As a result the element ratio for showing C/O in final product is 10.3, illustrates final production
Graphene oxygen content in thing is few；
(3) Raman spectrum is tested：As a result show respectively in about 1350cm-1And 1590cm-1Place occurs in that the D of graphene
The characteristic peak of band and E bands, D peaks represent SP3The vibration absorption peak of the bonding model of hydridization carbon, such as：" C-C ", " C-O ", " C=O ",
The area ratio of " O-C=O ", E bands and D bands is 12.1, illustrates that the defect of final product is seldom；
(4) microscope is detected：From SEM and transmission electron microscope result, the structure of final product
It is laminar structured, size is at tens nanometers to hundreds of nanometers, with reference to the Electron microscopy knot that resolution ratio is 0.2nm
Really, SEAD figure result and AFM test result, it is known that the piece number of plies of final product≤7 layers.
Embodiment 7
A kind of method for preparing graphene by micro crystal graphite batch, methods described step is as follows：
(1) by 1g micro crystal graphites powder, 0.1g cetyl trimethylammonium bromides and 1000mL solvent 1 in beaker magnetic
Power stirring 5h is well mixed, and obtains the suspension 1 of black, wherein, the concentration of micro crystal graphite is 1mg mL-1；The solvent 1 is by N-
Methyl pyrrolidone, DMAC N,N' dimethyl acetamide and o-dichlorohenzene are successively with volume ratio 0.5:0.5:2 mix；
(2) the ultrasonically treated 9h of suspension 1 for obtaining step (1), ultrasonic power is 1000W, obtains the suspension of black
2；
(3) suspension 2 for obtaining step (2) crushes stripping 7h, the work(of eddy current type crusher in eddy current type crusher
Rate is 4800W, obtains the suspension 3 of black；
(4) suspension 3 for obtaining step (3) ultrasonically treated 12h in ice-water bath, ultrasonic power is 1200W, obtains black
The suspension 4 of color；
(5) suspension 4 for obtaining step (4) is transferred in 100mL centrifuge tube, with 8000 revs/min of rotating speed from
Heart 60min, supernatant liquor is reclaimed, so that the stripping of next group micro crystal graphite is used, and is collected lower sediment, is obtained precipitation 1；
(6) precipitation 1 for obtaining step (4) is added in 1000mL absolute ethyl alcohol, and what is obtained after ultrasonic disperse is homogeneous
Suspension 5-1, be transferred in 50mL centrifuge tube, 10min centrifuged with 11000 revs/min of rotating speed, supernatant liquor is returned
Receive, collect lower sediment；Repeat it is described operation once, will this step collect lower sediment addition 1000mL absolute ethyl alcohol
In, the homogeneous suspension 5-2 obtained after ultrasonic disperse is transferred in 50mL centrifuge tube, with 11000 revs/min turn
Speed centrifugation 10min, supernatant liquor is reclaimed, lower sediment is collected, obtains precipitation 2；
(7) precipitation 2 obtained step (6) is added in 800mL distilled water, obtains homogeneous suspended after ultrasonic disperse
Liquid 6-1, is transferred in 50mL centrifuge tube, centrifuges 10min with 10000 revs/min of rotating speed, supernatant liquor is outwelled, under collection
Layer precipitation；Repeat it is described operation once, will this step collect lower sediment add 800mL distilled water in, through ultrasound divide
Homogeneous suspension 6-2 is obtained after dissipating, is transferred in 50mL centrifuge tube, 10min is centrifuged with 10000 revs/min of rotating speed, is fallen
Fall supernatant liquor, collect lower sediment, obtain precipitation 3；
(8) precipitation 3 for obtaining step (7) is added in 20mL distilled water, obtains homogeneous after ultrasonic disperse 5min
Suspension 7, ultrasonic power is 400W, and suspension 7 is frozen into solid in liquid nitrogen, and then room temperature in vacuo is dried, and vacuum is 8
~12MPa, obtains final product.
Obtained final product is detected as follows：
(1) X-ray powder diffraction is tested：As a result it is as shown in Figure 1, it can be seen that 25 ° of the characteristic peak of micro crystal graphite alkene, explanation
Micro crystal graphite is transformed to micro crystal graphite alkene, and final product is micro crystal graphite alkene；
(2) x-ray photoelectron power spectrum is tested：As a result the element ratio for showing C/O in final product is 9.1, illustrates final production
Graphene oxygen content in thing is few；
(3) Raman spectrum is tested：As a result show respectively in about 1350cm-1And 1590cm-1Place occurs in that the D of graphene
The characteristic peak of band and E bands, D peaks represent SP3The vibration absorption peak of the bonding model of hydridization carbon, such as：" C-C ", " C-O ", " C=O ",
The area ratio of " O-C=O ", E bands and D bands is 9.8, illustrates that the defect of final product is seldom；
(4) microscope is detected：From SEM and transmission electron microscope result, the structure of final product
It is laminar structured, size is at tens nanometers to hundreds of nanometers, with reference to the Electron microscopy knot that resolution ratio is 0.2nm
Really, SEAD figure result and AFM test result, it is known that the piece number of plies of final product≤7 layers.
Embodiment 8
A kind of method for preparing graphene by micro crystal graphite batch, methods described step is as follows：
(1) by 8g micro crystal graphites powder, 0.6g cetyl trimethylammonium bromides and 4000mL solvent 1 in beaker magnetic
Power stirring 10h is well mixed, and obtains the suspension 1 of black, wherein, the concentration of micro crystal graphite is 2mg mL-1；The solvent 1 by
1-METHYLPYRROLIDONE, DMAC N,N' dimethyl acetamide, butyrolactone and o-dichlorohenzene are successively with volume ratio 1:1:1:1 mixes；
(2) the ultrasonically treated 16h of suspension 1 for obtaining step (1), ultrasonic power is 2000W, obtains the suspension of black
2；
(3) suspension 2 for obtaining step (2) crushes stripping 8h, the work(of eddy current type crusher in eddy current type crusher
Rate is 5000W, obtains the suspension 3 of black；
(4) suspension 3 for obtaining step (3) ultrasound 18h in ice-water bath, ultrasonic power is 800W, obtains black
Suspension 4；
(5) suspension 4 for obtaining step (4) is transferred in 200mL centrifuge tube, with 9500 revs/min of rotating speed from
Heart 45min, supernatant liquor is reclaimed, so that the stripping of next group micro crystal graphite is used, and is collected lower sediment, is obtained precipitation 1；
(6) precipitation 1 for obtaining step (5) is added in 2000mL absolute ethyl alcohol, and what is obtained after ultrasonic disperse is homogeneous
Suspension 5-1, be transferred in 150mL centrifuge tube, 30min centrifuged with 9000 revs/min of rotating speed, supernatant liquor is returned
Receive, collect lower sediment；Repeat it is described operation once, will this step collect lower sediment addition 2000mL absolute ethyl alcohol
In, the homogeneous suspension 5-2 obtained after ultrasonic disperse is transferred in 150mL centrifuge tube, with 9000 revs/min turn
Speed centrifugation 30min, supernatant liquor is reclaimed, lower sediment is collected, obtains precipitation 2；
(7) precipitation 2 for obtaining step (6) is added in 1500mL distilled water, and homogeneous hang is obtained after ultrasonic disperse
Turbid liquid 6-1, is transferred in 150mL centrifuge tube, centrifuges 20min with 8000 revs/min of rotating speed, outwells supernatant liquor, collects
Lower sediment；Repeat it is described operation once, will this step collect lower sediment addition 1500mL distilled water in, through ultrasound
Homogeneous suspension 6-2 is obtained after scattered, is transferred in 150mL centrifuge tube, 20min is centrifuged with 8000 revs/min of rotating speed,
Supernatant liquor is outwelled, lower sediment is collected, obtains precipitation 3；
(8) precipitation 3 for obtaining step (7) is added in 80mL distilled water, obtains homogeneous after ultrasonic disperse 13min
Suspension 7, ultrasonic power is 400W, and suspension 7 is frozen into solid in liquid nitrogen, and then room temperature in vacuo is dried, and vacuum is 8
~12MPa, obtains final product.
Obtained final product is detected as follows：
(1) X-ray powder diffraction is tested：As a result it is as shown in Figure 1, it can be seen that 25 ° of the characteristic peak of micro crystal graphite alkene, explanation
Micro crystal graphite is transformed to micro crystal graphite alkene, and final product is micro crystal graphite alkene；
(2) x-ray photoelectron power spectrum is tested：As a result the element ratio for showing C/O in final product is 9.6, illustrates final production
Graphene oxygen content in thing is few；
(3) Raman spectrum is tested：As a result show respectively in about 1350cm-1And 1590cm-1Place occurs in that the D of graphene
The characteristic peak of band and E bands, D peaks represent SP3The vibration absorption peak of the bonding model of hydridization carbon, such as：" C-C ", " C-O ", " C=O ",
The area ratio of " O-C=O ", E bands and D bands is 10.4, illustrates that the defect of final product is seldom；
(4) microscope is detected：From SEM and transmission electron microscope result, the structure of final product
It is laminar structured, size is at tens nanometers to hundreds of nanometers, with reference to the Electron microscopy knot that resolution ratio is 0.2nm
Really, SEAD figure result and AFM test result, it is known that the piece number of plies of final product≤7 layers.
Embodiment 9
A kind of method for preparing graphene by micro crystal graphite batch, methods described step is as follows：
(1) by 20g micro crystal graphites powder, 2g cetyl trimethylammonium bromides and 5000mL solvent 1 in beaker magnetic
Power stirring 11h is well mixed, and obtains the suspension 1 of black, wherein, the concentration of micro crystal graphite is 4mg mL-1；The solvent 1 by
1-METHYLPYRROLIDONE and o-dichlorohenzene are with volume ratio 1:2 mix；
(2) the ultrasonically treated 18h of suspension 1 for obtaining step (1), ultrasonic power is 3000W, obtains the suspension of black
2；
(3) suspension 2 for obtaining step (2) crushes stripping 11h, the work(of eddy current type crusher in eddy current type crusher
Rate is 6000W, obtains the suspension 3 of black；
(4) suspension 3 for obtaining step (3) ultrasonically treated 18h in ice-water bath, ultrasonic power is 2400W, obtains black
The suspension 4 of color；
(5) suspension 4 for obtaining step (4) is transferred in 300mL centrifuge tube, with 11000 revs/min of rotating speed from
Heart 50min, supernatant liquor is reclaimed, so that the stripping of next group micro crystal graphite is used, and is collected lower sediment, is obtained precipitation 1；
(6) precipitation 1 for obtaining step (5) is added in 2500mL absolute methanol, and what is obtained after ultrasonic disperse is homogeneous
Suspension 5-1, be transferred in 300mL centrifuge tube, 20min centrifuged with 11000 revs/min of rotating speed, supernatant liquor is returned
Receive, collect lower sediment；Repeat it is described operation once, will this step collect lower sediment addition 2500mL absolute methanol
In, the homogeneous suspension 5-2 obtained after ultrasonic disperse is transferred in 300mL centrifuge tube, with 11000 revs/min turn
Speed centrifugation 20min, supernatant liquor is reclaimed, lower sediment is collected, obtains precipitation 2；
(7) precipitation 2 for obtaining step (6) is added in 2500mL distilled water, and homogeneous hang is obtained after ultrasonic disperse
Turbid liquid 6-1, is transferred in 300mL centrifuge tube, centrifuges 25min with 9000 revs/min of rotating speed, outwells supernatant liquor, collects
Lower sediment；Repeat it is described operation once, will this step collect lower sediment addition 2500mL distilled water in, through ultrasound
Homogeneous suspension 6-2 is obtained after scattered, is transferred in 300mL centrifuge tube, 25min is centrifuged with 9000 revs/min of rotating speed,
Supernatant liquor is outwelled, lower sediment is collected, obtains precipitation 3；
(8) precipitation 3 for obtaining step (7) is added in 150mL distilled water, obtains homogeneous after ultrasonic disperse 30min
Suspension 7, ultrasonic power is 800W, and suspension 7 is frozen into solid in liquid nitrogen, then room temperature in vacuo dry, vacuum
For 8~12MPa, final product is obtained.
Obtained final product is detected as follows：
(1) X-ray powder diffraction is tested：As a result it is as shown in Figure 1, it can be seen that 25 ° of the characteristic peak of micro crystal graphite alkene, explanation
Micro crystal graphite is transformed to micro crystal graphite alkene, and final product is micro crystal graphite alkene；
(2) x-ray photoelectron power spectrum is tested：As a result the element ratio for showing C/O in final product is 9.7, illustrates final production
Graphene oxygen content in thing is few；
(3) Raman spectrum is tested：As a result show respectively in about 1350cm-1And 1590cm-1Place occurs in that the D of graphene
The characteristic peak of band and E bands, D peaks represent SP3The vibration absorption peak of the bonding model of hydridization carbon, such as：" C-C ", " C-O ", " C=O ",
The area ratio of " O-C=O ", E bands and D bands is 11.2, illustrates that the defect of final product is seldom；
(4) microscope is detected：From SEM and transmission electron microscope result, the structure of final product
It is laminar structured, size is at tens nanometers to hundreds of nanometers, with reference to the Electron microscopy knot that resolution ratio is 0.2nm
Really, SEAD figure result and AFM test result, it is known that the piece number of plies of final product≤7 layers.
Embodiment 10
A kind of method for preparing graphene by micro crystal graphite batch, methods described step is as follows：
(1) by 0.5g micro crystal graphites powder, 0.05g cetyl trimethylammonium bromides and 5000mL solvent 1 in beaker
Middle magnetic agitation 2h is well mixed, and obtains the suspension 1 of black, wherein, the concentration of micro crystal graphite is 0.1mg mL-1；It is described molten
Agent 1 is by 1-METHYLPYRROLIDONE and o-dichlorohenzene with volume ratio 2:1 mixes；
(2) the ultrasonically treated 17h of suspension 1 for obtaining step (1), ultrasonic power is 1800W, obtains the suspension of black
2；
(3) suspension 2 for obtaining step (2) crushes stripping 10h, the work(of eddy current type crusher in eddy current type crusher
Rate is 6000W, obtains the suspension 3 of black；
(4) suspension 3 for obtaining step (3) ultrasonically treated 15h in ice-water bath, ultrasonic power is 2400W, obtains black
The suspension 4 of color；
(5) suspension 4 for obtaining step (4) is transferred in 300mL centrifuge tube, with 11000 revs/min of rotating speed from
Heart 10min, supernatant liquor is reclaimed, so that the stripping of next group micro crystal graphite is used, and is collected lower sediment, is obtained precipitation 1；
(6) precipitation 1 for obtaining step (5) is added in 2500mL anhydrous isopropyl alcohol alcohol, is obtained after ultrasonic disperse
Homogeneous suspension 5-1, is transferred in 300mL centrifuge tube, and 25min is centrifuged with 10000 revs/min of rotating speed, and upper strata is clear
Liquid is reclaimed, and collects lower sediment；Repeat it is described operation once, will this step collect lower sediment addition 2500mL it is anhydrous
In isopropanol, the homogeneous suspension 5-2 obtained after ultrasonic disperse is transferred in 300mL centrifuge tube, with 10000 revs/min
The rotating speed centrifugation 25min of clock, supernatant liquor is reclaimed, lower sediment is collected, obtains precipitation 2；
(7) precipitation 2 for obtaining step (6) is added in 2500mL distilled water, and homogeneous hang is obtained after ultrasonic disperse
Turbid liquid 6-1, is transferred in 300mL centrifuge tube, centrifuges 20min with 8000 revs/min of rotating speed, outwells supernatant liquor, collects
Lower sediment；Repeat it is described operation once, will this step collect lower sediment addition 2500mL distilled water in, through ultrasound
Homogeneous suspension 6-2 is obtained after scattered, is transferred in 300mL centrifuge tube, 20min is centrifuged with 8000 revs/min of rotating speed,
Supernatant liquor is outwelled, lower sediment is collected, obtains precipitation 3；
(8) precipitation 3 for obtaining step (7) is added in 30mL distilled water, obtains homogeneous after ultrasonic disperse 20min
Suspension 7, ultrasonic power is 1200W, and suspension 7 is frozen into solid in liquid nitrogen, and then room temperature in vacuo is dried, and vacuum is
8~12MPa, obtains final product.
Obtained final product is detected as follows：
(1) X-ray powder diffraction is tested：As a result it is as shown in Figure 1, it can be seen that 25 ° of the characteristic peak of micro crystal graphite alkene, explanation
Micro crystal graphite is transformed to micro crystal graphite alkene, and final product is micro crystal graphite alkene；
(2) x-ray photoelectron power spectrum is tested：As a result the element ratio for showing C/O in final product is 9.1, illustrates final production
Graphene oxygen content in thing is few；
(3) Raman spectrum is tested：As a result show respectively in about 1350cm-1And 1590cm-1Place occurs in that the D of graphene
The characteristic peak of band and E bands, D peaks represent SP3The vibration absorption peak of the bonding model of hydridization carbon, such as：" C-C ", " C-O ", " C=O ",
The area ratio of " O-C=O ", E bands and D bands is 10.1, illustrates that the defect of final product is seldom；
(4) microscope is detected：From SEM and transmission electron microscope result, the structure of final product
It is laminar structured, size is at tens nanometers to hundreds of nanometers, with reference to the Electron microscopy knot that resolution ratio is 0.2nm
Really, SEAD figure result and AFM test result, it is known that the piece number of plies of final product≤7 layers.
Embodiment 11
Embodiment 1~10 is obtained into final product, i.e. micro crystal graphite alkene, respectively as lithium after 120 DEG C of drying and processings
The negative material of battery, is assembled into a diameter of 2cm button cells respectively in glove box, is specially：Using metal lithium sheet as just
Pole active material, by negative active core-shell material micro crystal graphite alkene, binding agent Kynoar (PVDF), acetylene black with mass ratio 8:1:
1 ratio is well mixed, the even spread straticulation on copper foil, and disk is cut into as positive electrode, Celgard after drying
2300 be barrier film, 1.0mol/L LiPF6(EC and DMC volume ratio are 1 to/EC (ethylene carbonate)+DMC (dimethyl carbonate):
1) be electrolyte, be assembled into CR2032 button cells in argon gas glove box, and use LAND CT2001A test systems to
Embodiment 10 obtains the capacity property and cyclicity that button cell is made for negative active core-shell material for final product, i.e. micro crystal graphite alkene
Matter is tested, specific as follows：
Tested under 0.1A/g electric currents, the capacity of button cell is stable in 450mAh/g, and to during 100 circulations, knob
The capacity of button battery is not also significantly reduced；
From multiplying power test, when electric current is raised to 1000mAh/g, the capacity of button cell is stable in 350mAh/g, knob
Battery is detained under the conditions of more high current density, such as 5A/g, capacity remains to reach 200mAh/g, illustrates at higher current densities, knob
Button battery, which completes a charge and discharge process, only needs 2min, and the final product has fast charging and discharging feature, is suitable for actual answer
With.
Use LAND CT2001A test systems respectively to obtaining final product with embodiment 1~9, i.e. micro crystal graphite alkene is
The capacity property and recursive nature that button cell is made in negative active core-shell material are tested, as a result with being obtained finally with embodiment 10
Product, i.e. micro crystal graphite alkene are that the capacity property of the obtained button cell of negative active core-shell material is similar with recursive nature test result.
The present invention include but is not limited to above example, it is every carried out under the principle of spirit of the present invention it is any equivalent
Replace or local improvement, all will be regarded as within protection scope of the present invention.
Claims (7)
1. a kind of method that graphene is prepared by micro crystal graphite batch, it is characterised in that：Step is as follows：
(1) micro crystal graphite powder, surfactant and solvent 1 are well mixed, obtain suspension 1, wherein, micro crystal graphite it is dense
Spend for 0.1mg mL-1~5mg mL-1；
Surfactant is cetyl trimethylammonium bromide, lauryl sodium sulfate, sldium lauryl sulfate or polyvinyl pyrrole
Alkanone；Solvent 1 is the mixed solution of organic reagent and o-dichlorohenzene, and organic reagent is 1-METHYLPYRROLIDONE, N, N- dimethyl
Formamide, DMAC N,N' dimethyl acetamide and butyrolactone one or more therein；Micro crystal graphite and surfactant qualities
The ratio between be 10:1~20:1；
(2) by the ultrasonically treated 5h~20h of suspension 1, ultrasonic power is 200W~3200W, obtains suspension 2；
(3) by suspension 2 in eddy current type crusher, crush and peel off 5h~12h, the power of eddy current type crusher for 4000W~
6000W, obtains suspension 3；
(4) by suspension 3 in 0 DEG C~5 DEG C ultrasonically treated 5h~20h, ultrasonic power be 200W~3200W, obtain suspension
4；
(5) suspension 4 is centrifuged, collects lower sediment, obtain precipitation 1；
(6) precipitation 1 is distributed in solvent 2 and forms homogeneous suspension 5, centrifuged, collected lower sediment, obtain precipitation 2；
The solvent 2 is absolute ethyl alcohol, methanol, isopropanol or normal propyl alcohol；
(7) precipitation 2 is distributed in water and forms homogeneous suspension 6, centrifuged, collected lower sediment, obtain precipitation 3；
(8) precipitation 3 is distributed in water and forms homogeneous suspension 7, suspension 7 is frozen into solid in≤10min, then vacuum is dry
It is dry, obtain micro crystal graphite alkene.
2. a kind of method that graphene is prepared by micro crystal graphite batch according to claim 1, it is characterised in that：Step
(1) in, the volume ratio of organic reagent and o-dichlorohenzene is 3:1~1:3；2h~12h is mixed using magnetic agitation.
3. a kind of method that graphene is prepared by micro crystal graphite batch according to claim 1, it is characterised in that：Step
(4) in, by suspension 3 in ice-water bath it is ultrasonically treated.
4. a kind of method that graphene is prepared by micro crystal graphite batch according to claim 1, it is characterised in that：Step
(5) in, the rotating speed of centrifugation is 8000 revs/min~11000 revs/min, centrifuges 15min~60min.
5. a kind of method that graphene is prepared by micro crystal graphite batch according to claim 1, it is characterised in that：Step
(6) in, it is centrifuged after ultrasonic disperse；The rotating speed of centrifugation is 7000 revs/min~11000 revs/min, centrifugation
10min~30min；Step (6) is carried out >=2 times.
6. a kind of method that graphene is prepared by micro crystal graphite batch according to claim 1, it is characterised in that：Step
(7) in, the purity of water is water more than distilled water purity；It is centrifuged after ultrasonic disperse, the rotating speed of centrifugation is
7000 revs/min~10000 revs/min, centrifuge 10min~30min；Step (7) is carried out >=2 times.
7. a kind of method that graphene is prepared by micro crystal graphite batch according to claim 1, it is characterised in that：Step
(8) in, water is the water more than distilled water purity；Ultrasonic disperse, ultrasonic power be 200W~1000W, ultrasonic 10min~
30min；Freezed using liquid nitrogen.
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| CN105448618B (en) * | 2015-12-31 | 2018-06-29 | 南京萨特科技发展有限公司 | A kind of high-tension fuse of graphene arc extinguishing and preparation method thereof |
| CN105776194B (en) * | 2016-02-29 | 2017-09-05 | 成都新柯力化工科技有限公司 | A kind of preparation method of graphene microchip composite for 3D printing |
| CN106744913A (en) * | 2017-03-28 | 2017-05-31 | 上海理工大学 | A kind of method that utilization cryptocrystalline graphite largely prepares graphene oxide quantum dot |
| 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 |
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