CN106809824A - The method that two-step method prepares modified graphene - Google Patents
The method that two-step method prepares modified graphene Download PDFInfo
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- CN106809824A CN106809824A CN201710112271.XA CN201710112271A CN106809824A CN 106809824 A CN106809824 A CN 106809824A CN 201710112271 A CN201710112271 A CN 201710112271A CN 106809824 A CN106809824 A CN 106809824A
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Abstract
The present invention proposes a kind of method that two-step method prepares modified graphene, belongs to carbon nanomaterial technical field, and the method process is simple, production efficiency is high, and preparation-obtained modified graphene quality is higher, is worth with scientific research higher and production application.The technical scheme includes being added to graphite and mill ball in ball mill, and modifying agent is continuously added under ventilation condition, starts ball mill and starts reaction；After reaction terminates, stop ball mill, when ball grinder interior temperature is down to room temperature, add solvent to be mixed, be then again started up ball mill and start reaction；After reaction terminates, stop ball mill, collect the mixed slurry of mill ball and Graphene, sieving cleaning obtains modified graphene.The present invention can be applied in the preparation of modified few layer graphene.
Description
Technical field
The invention belongs to carbon nanomaterial technical field, more particularly to a kind of method that two-step method prepares modified graphene.
Background technology
Graphene is a kind of advanced nano-carbon material for receiving much concern in recent years, and it has bigger serface, high activity, height
The characteristics of degree modifiability and sheet two-dimensional structure, there is huge application to dive in fields such as the energy, environment, coating, sensors
Power.For example, in new energy field, Graphene has very big potentiality on the directions such as conductive additive, photovoltaic generation；In electric heating
Field, the flexibility of Graphene, low-power heat generation, and can be developed with the compound ability of other materials various
New product.
Current Graphene mass technology of preparing is more expensive to manufacture, processing step is more, inefficiency, and its low cost is controllable
Preparation is the pain spot of industrial circle all the time.At present, though declaring to have built kiloton even the Graphene production line of ton in industry,
The number of plies, performance and the property modifying functional group of Graphene can not be still accurately controlled, and this really determines stone in many practical applications
The key factor of black alkene application effect and prospect.Similar method appears in Americana (I.- in 2012 first
Y.Jeon, etc. " Edge-carboxylated graphene nanosheets via ball milling ", PNAS 109,
5588-5593,2012.) in, method directly carries out dry ball milling with dry ice in text, and what is obtained is the graphite particle of pulverization, but
Its thickness can not still be referred to as Graphene more than 1 micron.Proposed in coherent reference patent such as Chinese patent 201610436747.0
The Graphene of micron-scale is obtained by the way of addition dry ice carries out ball milling, but still cannot have been peeled off into thickness existing
The thin layer of below 3nm, and in the industry it is generally recognized that only can just be referred to as Graphene within this thickness.Chinese patent
Proposition carries out ball milling preparation with surfactant in CN103466608B, but the method to prepare yield relatively low, need to by a high speed from
The heart is separated, and can just obtain the satisfactory grapheme material of small part.Proposed in solvent in Chinese patent 201610513161.X
In carry out again after ultrasonic stripping the method for ball milling and prepare Graphene, but this method cannot obtain modifying and decorating functional group,
Ultrasonic procedure is highly energy-consuming, inefficient reaction method simultaneously, it is difficult to meet the demand of downstream application.
The content of the invention
The present invention proposes a kind of method that two-step method prepares modified graphene, and the method process is simple, production efficiency is high, leads to
Crossing two-step method can directly prepare the modified graphene of high-quality, be worth with scientific research higher and production application.
In order to achieve the above object, the present invention proposes a kind of method that two-step method prepares modified graphene, including following
Step：
Graphite and mill ball are added in ball mill, modifying agent is continuously added under ventilation condition, started ball mill and open
Begin to react；
After reaction terminates, stop ball mill, when ball grinder interior temperature is down to room temperature, add solvent to be mixed, so
After be again started up ball mill start reaction；
After reaction terminates, stop ball mill, collect the mixed slurry of mill ball and Graphene, sieving cleaning is modified
Graphene.
Used as optimal technical scheme, the weight ratio of the graphite for being added and mill ball is 1:30-1:100.
Used as optimal technical scheme, the weight ratio of the graphite for being added and modifying agent is 20:1-1:20.
Used as optimal technical scheme, the solvent for being added is 1 with the weight ratio of graphite:5-1:20.
Used as optimal technical scheme, set rotating speed is 100-300rpm, ball milling after addition modifying agent startup ball mill
Time is 12-72 hours；Set rotating speed is 300-500rpm after addition solvent startup ball mill, and Ball-milling Time is that 4-48 is small
When.
As optimal technical scheme, the mill ball be zirconium oxide abrasive ball, from a diameter of 0.5mm-5mm at least
A kind of zirconium oxide abrasive ball.
Used as optimal technical scheme, the modifying agent is selected from the oxidisability that can be reacted with graphite under ball milling condition
Any one in reagent, small molecule coupling agent or macromolecule polyalcohol.
As optimal technical scheme, the solvent be selected from water, methyl alcohol, ethanol, dimethylformamide, methyl pyrrolidone,
At least one in benzene or toluene.
Present invention also offers the side that a kind of two-step method as described in above-mentioned any one technical scheme prepares modified graphene
The modified graphene that method is prepared.
Used as optimal technical scheme, the number of plies of the modified graphene is less than 10 layers, and thickness is no more than 3nm.
Compared with prior art, advantages and positive effects of the present invention are：
1st, method provided by the present invention using it is modified be continuously finished in same equipment with stripping two-step reaction by the way of,
Two kinds of technological advantages are peeled off by combining Rapid Modification graphite edge and high efficiency, can directly be obtained without complicated technology and equipment
To the modified graphene material of high-quality；
2nd, present invention process and equipment are very simple, can complete modified without more exchange device and peel off two-step reaction, do not have
There are the processes such as intermediate transfer, cleaning, drying, significantly improve production efficiency, reduce energy consumption, and chemicals during greatly reducing
Pollution；
3rd, method provided by the present invention safety non-toxic and without the useless solid discharge of waste liquid waste gas in whole process, accords with completely
Cyclization guaranteed request；
4th, method provided by the present invention, compared to existing process, can substantially reduce the production time, can batch metaplasia
Produce, directly obtain the modified graphene slurry for downstream product application, or by being dried to obtain modified graphene powder.
Brief description of the drawings
Carboxyl and the schematic diagram of hydroxyl edge modified graphene that Fig. 1 is provided by the embodiment of the present invention 1；
Carboxyl and the Electronic Speculum schematic diagram of hydroxyl edge modified graphene that Fig. 2 is provided by the embodiment of the present invention 1, wherein,
3000 times of multiplication factor, 2 μm of resolution ratio, scanning voltage 15kV；
Carboxyl and the Electronic Speculum schematic diagram of hydroxyl edge modified graphene that Fig. 3 is provided by the embodiment of the present invention 1, wherein,
40000 times of multiplication factor, resolution ratio 200nm, scanning voltage 15kV；
Carboxyl and the Electronic Speculum schematic diagram of hydroxyl edge modified graphene that Fig. 4 is provided by the embodiment of the present invention 1, wherein,
30000 times of multiplication factor, resolution ratio 200nm, scanning voltage 15kV.
Specific embodiment
The technical scheme in the embodiment of the present invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of embodiment of the invention, rather than whole embodiments.Based on the embodiment in the present invention, this area is common
The every other embodiment that technical staff is obtained under the premise of creative work is not made, belongs to the model of present invention protection
Enclose.
A kind of method that two-step method prepares modified graphene is the embodiment of the invention provides, is comprised the following steps：
S1：Graphite and mill ball are added in ball mill, modifying agent is continuously added under ventilation condition, start ball mill
Start reaction；
In this step, graphite, mill ball and modifying agent are added in ball mill according to sequencing and are reacted,
Wherein, graphite is first mixed with modifying agent, primarily to according to different application needs, first being carried out soon to graphite edge
Speed modification, by graft active function groups, is conducive to being obtained after subsequent ball milling is peeled off the modified graphite of estimated performance
Alkene.
It is understood that in this step, by the modifying agent for being added is volatile materials, it is therefore desirable in ventilation
Under the conditions of to modifying agent is added in ball mill, be beneficial to the holding of operation environment.In addition, in this step, for being made
Ball mill is simultaneously not specifically limited, and can be planetary ball mill or sand mill, high rigidity mill ball etc., art technology
Personnel can be selected according to practical operation condition.
S2：After reaction terminates, stop ball mill, when ball grinder interior temperature is down to room temperature, add solvent to be mixed,
Then it is again started up ball mill and starts reaction；
In this step, in treating that S1 step reactions terminate, solvent need to be further added to be carried out with previous reaction gained material
Mixing, mainly uses solvent to carry out ball milling stripping to the graphite of the foregoing active function groups of graft here, pre- to obtain
The modified graphene of phase high-quality.
It should be noted that in treating that S1 step reactions terminate, the temperature of ball grinder interior, pressure are higher, for not shadow
The addition of solvent is rung, it is necessary to temperature, pressure to ball grinder interior are adjusted after above-mentioned steps terminate, for example, can lead to
The vent valve for crossing opening ball mill is depressurized, and when it is down to 1 standard atmospheric pressure, ball mill is opened to be carried out suitably clearly
Reason, now can carry out forced cooling by the way of the immersion of outside, the temperature of ball grinder interior is reduced near room temperature.
It is understood that in step S1 and S2, it is necessary to ball mill sealing is solid before starting ball mill and starting reaction
Determine, restart after the pressure limiting valve and emergent air-release valve on ball mill to be confirmed are in shape.In addition, starting ball mill
Afterwards, it is necessary to observe the pressure of ball grinder interior, for example can be after ball mill be started in 10 minutes or so observed and recorded ball mills
Portion's pressure, then every 2 hour record ball grinder interior pressure, it is ensured that pressure is no more than 6MPa.
S3：After reaction terminates, stop ball mill, collect the mixed slurry of mill ball and Graphene, sieving cleaning is changed
Property Graphene.
In this step, after above-mentioned reaction terminates, special collection cleaning plant is can be used to collect resulting grinding
The mixed slurry of ball and Graphene, wherein, mentioned special collector can collect cleaning plant for conventional, as long as its material
The performance of the slurry obtained by not influenceing.
The preparation method of the modified graphene provided by the above embodiment of the present invention is existed using modified with stripping two-step reaction
The mode being continuously finished in same equipment, two kinds of technological advantages, nothing are peeled off by combining Rapid Modification graphite edge and high efficiency
The modified graphene material of high-quality is directly obtained by needing complicated technology and equipment, can be for subsequent storage, transport, using offer
It is convenient.
In a preferred embodiment, the graphite and the weight ratio of mill ball for being added are 1:30-1:100.In the present embodiment
In, the weight ratio of graphite and mill ball is specifically defined, this is primarily to ensure that mill ball can play good to graphite
Ball action.It is understood that the weight ratio of the graphite for being added and mill ball can also be 1:40、1:50、1:60、1:
70、1:80、1:90 etc., those skilled in the art can need to be selected according to practical operation.It will also be appreciated that for upper
State for method, the purpose for adding mill ball is, in order to play ball action to graphite, for graphite, to grind
The addition of ball not key factor, the weight of the mill ball that will can be added is limited within the above range, also may be used
With beyond the scope, but it should be recognized that when the weight of the mill ball for being added exceeds above range, though class can be prepared
Like product, but production efficiency can be caused to substantially reduce.
In a preferred embodiment, the graphite and the weight ratio of modifying agent for being added are 20:1-1:20.In the present embodiment
In, the weight ratio of graphite and modifying agent is specifically defined, this is primarily to ensure that modifying agent can fill to graphite edge
Divide and be effectively modified.It is understood that the weight ratio of the graphite for being added and modifying agent can also be 15:1、10:1、2:1、
1:1、1:5、1:10、1:15 etc., those skilled in the art can need to be selected according to practical operation.It will also be appreciated that
For the above method, the purpose for adding modifying agent is effectively modified in order to be played to graphite, therefore will can be added
The weight of mill ball is limited within the above range.But it should be recognized that the weight ratio of the graphite for being added and modifying agent also may be used
Beyond the scope, more or less, but the cost performance and production efficiency of preparation-obtained similar products can not show a candle to by this reality
The weight of example restriction is applied than the product for preparing.
In a preferred embodiment, the solvent for being added is 1 with the weight ratio of graphite:5-1:20.In the present embodiment, have
Body defines the weight ratio of added solvent and graphite, to ensure the abundant reaction of graphite and solvent.It is understood that this
Aforementioned proportion in embodiment not to being added is specifically limited, as long as being able to ensure that added solvent liquid level there was not stone
Ink, can fully react.It is understood that the solvent for being added can also be 1 with the weight ratio of graphite:10、
1:15 etc., those skilled in the art can need to be selected according to practical operation.
In a preferred embodiment, rotating speed set after addition modifying agent startup ball mill is 100-300rpm, ball milling
Time is 12-72 hours；Set rotating speed is 300-500rpm after addition solvent startup ball mill, and Ball-milling Time is that 4-48 is small
When.In the present embodiment, rotating speed and Ball-milling Time after starting to the ball mill in modified and ball milling strip step are carried out
Limit, this is primarily to Rapid Modification graphite edge and advantage of both high efficiency stripping can be reached.It is appreciated that
, after adding modifying agent to start ball mill set rotating speed can also for 150,200,250rpm etc., Ball-milling Time is also
It can be 15,20,30,40,50,60,70 hours etc.；Set rotating speed can also be after adding solvent to start ball mill
350th, 400,450rpm etc., Ball-milling Time can also be 1,5,10,15,20,25,30,35,40,45 hours etc., art technology
Personnel can need to be selected according to practical operation.
In a preferred embodiment, the mill ball be zirconium oxide abrasive ball, from a diameter of 0.5mm-5mm at least
A kind of zirconium oxide abrasive ball.In the present embodiment, selected mill ball is any combination of the mill ball of different-diameter, this master
If in order to farthest that graphite grinding is abundant.Can be the group of 1mm, 2mm and 5mm for the combination of mill ball
Close, or 0.5mm, 1mm and 2mm combination, or 0.5mm, 1mm, 2mm and 5mm combination, or 0.5mm, 1mm and 5mm
Combination.The ratio of the mill ball of each diameter is suitable in any combination, such as the weight of three in the combination of 1mm, 2mm and 5mm
Amount ratio can be 3:1:1,0.5mm, the weight ratio of three can be 2 in the combination of 1mm and 2mm:1:1,0.5mm, 1mm, 2mm and
Four weight ratio can be 2 in the combination of 5mm:1:1:1,0.5mm, the weight ratio of the combination three of 1mm and 5mm can be 3:
1:1.For each diameter grinding ball in the composition and composition of the diameter of mill ball weight than selection in the present embodiment not
It is specifically limited, those skilled in the art can need to be selected according to practical operation.
In an alternative embodiment, the modifying agent is selected from the oxidisability that can be reacted with graphite under ball milling condition
Any one in reagent, small molecule coupling agent or macromolecule polyalcohol.Wherein, oxidative reagent can include dry ice, nanometer
TiO2, small molecule coupling agent can be silane coupler, and macromolecule polyalcohol can be polystyrene, polyacrylamide etc..
In another alternative embodiment, the solvent is selected from water, methyl alcohol, ethanol, dimethylformamide, methyl pyrrolidone, benzene or toluene
In at least one.Used modifying agent and solvent is specifically listed in above-described embodiment, graphite graft can be conducive to
Active function groups and the follow-up active force for opening piece interlayer make it obtain good ball milling stripping, so as to prepare expected layer
The modified graphene of number and performance.It is understood that above-described embodiment is not limited to cited modifying agent and solvent, also
Can be that those skilled in the art carry out the reasonable other materials replaced with reference to common knowledge.
The embodiment of the present invention additionally provides a kind of two-step method as described in above-mentioned any one embodiment and prepares modified graphene
The modified graphene for preparing of method.The modified graphene quality prepared by above-described embodiment is higher, and its slurry can
Downstream product is directly applied to, or by being dried to obtain modified graphene powder, so as to be conducive to subsequent storage, transport, application.
In a preferred embodiment, the number of plies of the modified graphene is less than 10 layers, and thickness is no more than 3nm.In this implementation
In example, because the number of plies and thickness of resulting modified graphene are satisfied by standard, it will thus be appreciated that having prepared true
Positive grapheme material, is worth with scientific research higher and production application.
It is understood that the modified graphene that the present invention can be prepared is not limited to cited by above-described embodiment
, this is primarily due to that by the modified of different active function groups the modified graphite that different edges are modified can be prepared
Alkene, therefore, when selected active function groups are different, the structure of the prepared modified graphene for arriving, property and application
Also and differ, those skilled in the art can be according to different needs, and it is corresponding to prepare to select different active function groups
Different modified graphenes.
The method that the two-step method provided to become apparent from introducing in detail the embodiment of the present invention prepares modified graphene, under
Face will be described in conjunction with specific embodiments.
Embodiment 1
The zirconium oxide abrasive ball of a diameter of 1mm, 2mm, 5mm is selected, weight ratio is 3:1:1,100g graphite and 3kg are ground
(weight ratio is 1 to ball:30) after mixing in addition ball mill.In fume hood, by 200g solid dry ices, (weight compares 2：1) ball is added
In grinding machine.After ball mill sealing is fixed, confirm that pressure limiting valve and emergent air-release valve on ball mill are in shape.Start ball
Grinding machine, speed setting is 300RPM, and Ball-milling Time is 24 hours.10 minutes observed and recorded ball grinder interior pressure after startup, with
Afterwards every 2 hour record ball grinder interior pressure, it is ensured that pressure is no more than 6MPa.After the completion of reaction, stop ball mill, open
Deflation valve, after ball grinder interior air pressure reaches 1atm, opens ball mill, is suitably cleared up, can be using outside immersion
Method carries out forced cooling.When ball grinder interior temperature is reduced near room temperature, 500ml methyl pyrrolidones are added as molten
Agent, appropriate stirring mixing.Ball mill is again sealed off to fix, starts ball mill, speed setting is 300RPM, and Ball-milling Time is 24
Hour.After the completion of reaction, stop ball mill, open ball mill suitably cleared up, with special collector by mill ball with
Graphene slurry takes out, and cleaning of sieving, you can obtain carboxyl and hydroxyl edge modified graphene, wherein, the modified graphene
The number of plies be less than 10 layers, thickness is no more than 3nm, and edge contains abundant hydrophilic functional group, and aqueous stability is good, solubility
It is high.
Embodiment 2
The zirconium oxide abrasive ball of a diameter of 0.5mm, 1mm, 2mm, 5mm is selected, weight ratio is 2:1:1:1, by 100g graphite
(weight compares 1 with 5kg mill balls:50) after mixing in addition ball mill.In fume hood, by 2000g solid dry ices, (weight compares 1:
20) with 10ml nano-TiOs2Alcohol dispersion liquid add ball mill in.After ball mill sealing is fixed, the limit on ball mill is confirmed
Pressure valve and emergent air-release valve are in shape.Start ball mill, speed setting is 100RPM, and Ball-milling Time is 72 hours.Open
10 minutes observed and recorded ball grinder interior pressure after dynamic, then every 2 hour record ball grinder interior pressure, it is ensured that pressure does not surpass
Cross 6MPa.After the completion of reaction, stop ball mill, ball mill is moved in fume hood, open deflation valve, treat ball grinder interior
After air pressure reaches 1atm, ball mill is opened, suitably cleared up, forced cooling can be carried out using the method for outside immersion.Treat ball
When grinding machine internal temperature is reduced near room temperature, add 500ml ethanol as solvent, be appropriately mixed with rod iron.By ball milling
Machine is again sealed off fixing, and starts ball mill, and speed setting is 500RPM, and Ball-milling Time is 4 hours.After the completion of reaction, stop
Ball mill, opens ball mill and is suitably cleared up, and is taken out mill ball and Graphene slurry with special collector, and it is clear to sieve
Wash, you can obtain TiO2Carboxyl edge modified graphene, wherein, the number of plies of the modified graphene is less than 10 layers, and thickness is no more than
3nm, TiO2Nano particle is uniformly distributed in graphene edge and surface.
Embodiment 3
The zirconium oxide abrasive ball of a diameter of 0.5mm, 1mm, 5mm is selected, weight ratio is 3:1:1, by 100g graphite and 10kg
(weight compares 1 to mill ball:100) after mixing in addition ball mill.In fume hood, by 5g silane KH-560 coupling agent (weight ratios
20:1) add in ball mill, add 50ml water as reaction promoter.After ball mill sealing is fixed, confirm on ball mill
Pressure limiting valve and emergent air-release valve are in shape.Start ball mill, speed setting is 300RPM, and Ball-milling Time is 24 hours.
10 minutes observed and recorded ball grinder interior pressure after startup, then every 2 hour record ball grinder interior pressure, it is ensured that pressure is not
More than 6MPa.After the completion of reaction, stop ball mill, ball mill is moved in fume hood, open deflation valve, treat in ball mill
After portion's air pressure reaches 1atm, ball mill is opened, suitably cleared up, forced cooling can be carried out using the method for outside immersion.Treat
When ball grinder interior temperature is reduced near room temperature, add 500ml water as solvent, be appropriately mixed with rod iron.By ball milling
Machine is again sealed off fixing, and starts ball mill, and speed setting is 300RPM, and Ball-milling Time is 48 hours.After the completion of reaction, stop
Ball mill, opens ball mill and is suitably cleared up, and is taken out mill ball and Graphene slurry with special collector, and it is clear to sieve
Wash, you can obtain being alkylated edge modified graphene, wherein, the number of plies of the modified graphene is less than 10 layers, and thickness is no more than
3nm, edge contains abundant alkyl functional group, and hydrophobicity is strong.
Embodiment 4
The zirconium oxide abrasive ball of a diameter of 0.5mm, 1mm, 5mm is selected, weight ratio is 3:1:1,100g graphite is ground with 5kg
(weight compares 1 to abrading-ball:50) after mixing in addition ball mill.In fume hood, by 25ml styrene and the DMF solution of isobutyl acylbromide
(weight compares 1:5) in addition ball mill.After quickly ball grinder sealing is fixed, the pressure limiting valve and emergency deflation on ball mill are confirmed
Valve is in shape.Start ball mill, speed setting is 100RPM, and Ball-milling Time is 72 hours.After the completion of reaction, stop
Ball mill, opens deflation valve, after ball grinder interior air pressure reaches 1atm, opens ball mill, is suitably cleared up, and can use
The method of outside immersion carries out forced cooling.When ball grinder interior temperature is reduced near room temperature, the isobutyl of 5ml azos two is added
Nitrile, as solvent, is appropriately mixed as radical polymerization initiator and 500ml methyl pyrrolidones with rod iron.By ball mill
It is again sealed off fixing, starts ball mill, speed setting is 300RPM, and Ball-milling Time is 48 hours.After the completion of reaction, ball is stopped
Grinding machine, opens ball mill and is suitably cleared up, and is taken out mill ball and Graphene slurry with special collector, and it is clear to sieve
Wash, you can obtain polystyrene edge modified graphene, wherein, the number of plies of the modified graphene is less than 10 layers, and thickness is no more than
3nm, edge contains polystyrene long-chain functional group, can be used for high strength composite preparation.
Embodiment 5
The zirconium oxide abrasive ball of a diameter of 1mm, 2mm, 5mm is selected, weight ratio is 3:1:1,100g graphite and 5kg are ground
(weight compares 1 to ball:50) after mixing in addition ball mill.In fume hood, by 10g acrylamide monomers and 0.5g ammonium persulfates
(weight compares 10:1) add in ball mill, add 100ml water.After ball grinder sealing is fixed, the pressure limiting on ball mill is confirmed
Valve and emergent air-release valve are in shape.Start ball mill, speed setting is 200RPM, and Ball-milling Time is 12 hours.Anti-
After should terminating, stop ball mill, open deflation valve, after ball grinder interior air pressure reaches 1atm, open ball mill, fitted
Work as cleaning, forced cooling can be carried out using the method for outside immersion.When ball grinder interior temperature is reduced near room temperature, add
500ml water is appropriately mixed as solvent with rod iron.Ball mill is again sealed off to fix, starts ball mill, speed setting is
300RPM, Ball-milling Time is 24 hours.After the completion of reaction, stop ball mill, open ball mill and suitably cleared up, with special
Collection device takes out mill ball and Graphene slurry, and cleaning of sieving, you can obtain polyacrylamide edge modified graphene,
Wherein, the modified graphene number of plies is less than 10 layers, and thickness is no more than 3nm, and edge contains polyacrylamide macromolecular chain, can be used for
It is prepared by further functionalization or composite.
Claims (10)
1. a kind of method that two-step method prepares modified graphene, it is characterised in that comprise the following steps：
Graphite and mill ball are added in ball mill, modifying agent is continuously added under ventilation condition, started ball mill and start instead
Should；
After reaction terminates, stop ball mill, when ball grinder interior temperature is down to room temperature, add solvent to be mixed, Ran Houzai
Secondary startup ball mill starts reaction；
After reaction terminates, stop ball mill, collect the mixed slurry of mill ball and Graphene, sieving cleaning obtains modified graphite
Alkene.
2. method according to claim 1, it is characterised in that the graphite and the weight ratio of mill ball for being added are 1:30-
1:100。
3. method according to claim 1, it is characterised in that the graphite and the weight ratio of modifying agent for being added are 20:1-
1:20。
4. method according to claim 1, it is characterised in that the solvent for being added is 1 with the weight ratio of graphite:5-1:
20。
5. method according to claim 1, it is characterised in that add modifying agent to start set rotating speed after ball mill to be
100-300rpm, Ball-milling Time is 12-72 hours；Set rotating speed is 300-500rpm after addition solvent startup ball mill,
Ball-milling Time is 4-48 hours.
6. method according to claim 1, it is characterised in that the mill ball is zirconium oxide abrasive ball, from a diameter of
At least one zirconium oxide abrasive ball in 0.5mm-5mm.
7. method according to claim 1, it is characterised in that the modifying agent be selected from can under ball milling condition with graphite
Any one in the oxidative reagent, small molecule coupling agent or the macromolecule polyalcohol that react.
8. method according to claim 1, it is characterised in that the solvent is selected from water, methyl alcohol, ethanol, dimethyl formyl
At least one in amine, methyl pyrrolidone, benzene or toluene.
9. a kind of two-step method as described in claim any one of 1-8 prepares the modified stone that the method for modified graphene is prepared
Black alkene.
10. modified graphene according to claim 9, it is characterised in that the number of plies of the modified graphene is less than 10 layers,
Thickness is no more than 3nm.
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