CN107364855B - A kind of preparation process improving graphene purity - Google Patents
A kind of preparation process improving graphene purity Download PDFInfo
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- CN107364855B CN107364855B CN201710799206.9A CN201710799206A CN107364855B CN 107364855 B CN107364855 B CN 107364855B CN 201710799206 A CN201710799206 A CN 201710799206A CN 107364855 B CN107364855 B CN 107364855B
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Abstract
The invention discloses a kind of preparation processes improving graphene purity, include the following steps：（1）Metallic catalyst, metal agent for capturing and carbon materials, glucan, vinyl acetate maleic anhydride multipolymer, starch acrylonitrile graft copolymer, cellulose graft acrylonitrile hydrolysis product are stirred, it is adsorbed, obtains the carbon source mixture for being adsorbed with metallic catalyst；（2）It is heated after reducing agent is mixed with the carbon source mixture for being adsorbed with metallic catalyst, obtains graphene first product；（3）Grinding；（4）It is put into graphene first product and magnetic draw point abrasive body in closed grinding container, grinding container is placed in transformation magnetic field space, is removed；（5）Draw point is detached, after settling, centrifuging, the graphene transperent suspension liquid of high-purity is made.Preparation process of the present invention is simple, and graphene purity is high, and yield is high, pollution-free.
Description
Technical field
The present invention relates to carbon material technical field, more particularly to a kind of preparation process improving graphene purity.
Background technology
Graphene (Graphene) is the only one layer of atomic thickness for being stripped out from graphite material, being made of carbon atom
Two dimensional crystal.2004, Univ Manchester UK physicist An Deliegaimu and Constantine's Nuo Woxiao loves,
Graphene is isolated in success from graphite, it was demonstrated that therefore it can also obtain Nobel's object in 2010 jointly with individualism, two people
Neo-Confucianism prize.Graphene is both most thin material, and most tough material, 200 times more taller than best steel of fracture strength.
It has good elasticity, stretch range that can reach the 20% of own dimensions again simultaneously.It is that current nature is most thin, intensity highest
Material, if making hammock with the graphene of one piece of 1 square metre of area, weight itself can bear one less than 1 milligram
One kilogram of cat.Graphene most potential application at present is the substitute as silicon, ultra micro transistor npn npn is manufactured, for producing
Following supercomputer.Replace silicon with graphene, the speed of service of computer processor will be hundreds times fast.In addition, graphite
Alkene is almost fully transparent, only absorbs 2.3% light.On the other hand, it is very fine and close, even minimum gas atom (helium
Atom) it can not also penetrate.These features make it be highly suitable as the raw material of transparent electron product, and such as transparent touch is shown
Screen, luminescent screen and solar panel.
As presently found most thin, maximum intensity, a kind of strongest novel nano-material of electrical and thermal conductivity performance, graphene
It is referred to as " dark fund ", is " king of new material ", scientist even foretells that graphene " will thoroughly change 21 century ".Very likely lift
Play a subversiveness new technology new industrial revolution have swept the globe.
Currently, a variety of methods, which can be used, is prepared grapheme material powder, as mechanical stripping method, oxidation-reduction method,
Crystal epitaxy method, chemical vapour deposition technique, organic synthesis method and stripping carbon nanotube method etc..In these methods, mechanical
Stripping method and epitaxial growth method preparation efficiency are very low, it is difficult to meet large-scale needs.Although chemical vapour deposition technique can obtain
The continuous graphene film of large scale is obtained, but is suitable for micro-nano electronic device or transparent conductive film, cannot but meet energy storage material
The extensive demand in material and functional composite material field.Oxidation-reduction method prepares grapheme material powder and is relatively easy to realize,
It is to prepare the common method of grapheme material powder, but this method uses a large amount of strong acid and oxygen during preparing graphene
Agent destroys seriously graphene surface, and is easy pollution environment, therefore is not suitable for the graphene system of extensive industrialization
It is standby.
On the basis of micromechanics stripping method, the grinding for being attempted to be carried out graphene with traditional ball grinding method is prepared greatly
The graphene or graphene oxide of amount, small area, Antisar M.V et al. have carried out wet ball grinding, have obtained thickness in water
The graphite nano-sheets of 10nm or more.In order to improve graphene charge stripping efficiency, people are assisted using a large amount of minute solid particles
Stripping process, with increase stripping process contact area and stripping number, but the removal of fine particle and liquid with detach, exist
Bigger difficulty.
The present invention provides a kind of preparation processes improving graphene purity.
Invention content
Technical problem to be solved by the present invention lies in：Provide a kind of preparation process improving graphene purity.
In order to solve the above technical problems, the present invention provides a kind of preparation process improving graphene purity, including it is following
Step：
（1）By metallic catalyst, metal agent for capturing and carbon materials, glucan, vinyl acetate-maleic anhydride copolymerization
Object, starch acrylonitrile graft copolymer, cellulose graft acrylonitrile hydrolysis product are stirred, and are adsorbed, are adsorbed with
The carbon source mixture of metallic catalyst；The metallic catalyst, metal agent for capturing and carbon materials, glucan, vinyl acetate-are suitable
Maleic anhydride copolymer, starch acrylonitrile graft copolymer, cellulose graft acrylonitrile hydrolysis product weight part ratio be 1：
（0.4-0.6）：（0.8-1.2）：（0.1-0.3）：（0.5-0.7）：（0.1-0.3）：（0.3-0.5）；
（2）By reducing agent and step（1）In be adsorbed with metallic catalyst carbon source mixture mixing after, according to heating speed
Rate is that be heated to temperature be 950-1050 DEG C to 12-14 DEG C/min, and constant temperature keeps 26-28h, obtains graphene first product；The reduction
Agent is Nano-Zinc powder；
（3）By step（2）Obtained graphene first product is ground, and it is 10000 mesh to reach granularity；
（4）By the graphene first product and magnetism draw point abrasive body after grinding, it is put into closed grinding container, grinding is held
Device merging has in the tubular transformation magnetic field space formed to EDS maps, carries out stripping 48-58h, Nano graphite is made after stripping
The mixture dry powder of microplate-graphene；
（5）By step（4）The mixture dry powder of graphite nano micro-flake-graphene obtained detaches draw point, by sedimentation, from
After heart separation, the graphene transperent suspension liquid of high-purity is made.
Further, the metallic catalyst is zinc molybdate.
Further, the metal agent for capturing is diethylene triamine pentamethylene phosphonic.
Further, the step（4）The material of middle grinding container is austenitic stainless steel.
Further, the step（4）The conversion frequency of middle transformation magnetic field space is 2600-2800r/min, and magnetic induction is strong
Degree is 0.8-0.9T.
Further, include the following steps：
（1）By metallic catalyst, metal agent for capturing and carbon materials, glucan, vinyl acetate-maleic anhydride copolymerization
Object, starch acrylonitrile graft copolymer, cellulose graft acrylonitrile hydrolysis product are stirred, and are adsorbed, are adsorbed with
The carbon source mixture of metallic catalyst；The metallic catalyst, metal agent for capturing and carbon materials, glucan, vinyl acetate-are suitable
Maleic anhydride copolymer, starch acrylonitrile graft copolymer, cellulose graft acrylonitrile hydrolysis product weight part ratio be 1：
0.5：1 ：0.2：0.6：0.2：0.4；
（2）By reducing agent and step（1）In be adsorbed with metallic catalyst carbon source mixture mixing after, according to heating speed
Rate is that be heated to temperature be 1000 DEG C to 13 DEG C/min, and constant temperature keeps 27h, obtains graphene first product；The reducing agent is Nano-Zinc
Powder；
（3）By step（2）Obtained graphene first product is ground, and it is 10000 mesh to reach granularity；
（4）By the graphene first product and magnetism draw point abrasive body after grinding, it is put into closed grinding container, grinding is held
Device merging has in the tubular transformation magnetic field space formed to EDS maps, carries out stripping 53h, it is micro- that Nano graphite is made after stripping
The mixture dry powder of piece-graphene；
（5）By step（4）The mixture dry powder of graphite nano micro-flake-graphene obtained detaches draw point, by sedimentation, from
After heart separation, the graphene transperent suspension liquid of high-purity is made.
Beneficial effects of the present invention：The present invention provides a kind of preparation process improving graphene purity, and preparation process is simple,
Graphene purity is high, and yield is high, and present invention process does not use the environmental pollutions such as strong acid or oxidant
Serious raw material the effects that by ion exchange, chelating, absorption, realizes uniform graphitization, improves graphitization
Degree, meanwhile, using superfine magnetic draw point as abrasive body, the impact force generated each other is minimum but collision frequency is very high,
Fine particle and liquid are further removed, the destruction of lattice due to collision to graphene can be effectively weakened, is suitble to just
For the stripping of flaky graphite, graphene purity is improved.
Specific implementation mode
Carry out the embodiment that the present invention will be described in detail below with reference to embodiment, whereby to the present invention how application technology hand
Section solves technical problem, and the realization process for reaching technique effect can fully understand and implement.
It should be noted that writing length to save specification, unnecessary repetition and waste are avoided, in the feelings not conflicted
Under condition, the features in the embodiments and the embodiments of the present application can be combined with each other.
A kind of preparation process improving graphene purity, includes the following steps：
（1）By metallic catalyst, metal agent for capturing and carbon materials, glucan, vinyl acetate-maleic anhydride copolymerization
Object, starch acrylonitrile graft copolymer, cellulose graft acrylonitrile hydrolysis product are stirred, and are adsorbed, are adsorbed with
The carbon source mixture of metallic catalyst；The metallic catalyst, metal agent for capturing and carbon materials, glucan, vinyl acetate-are suitable
Maleic anhydride copolymer, starch acrylonitrile graft copolymer, cellulose graft acrylonitrile hydrolysis product weight part ratio be 1：
（0.4-0.6）：（0.8-1.2）：（0.1-0.3）：（0.5-0.7）：（0.1-0.3）：（0.3-0.5）；
（2）By reducing agent and step（1）In be adsorbed with metallic catalyst carbon source mixture mixing after, according to heating speed
Rate is that be heated to temperature be 950-1050 DEG C to 12-14 DEG C/min, and constant temperature keeps 26-28h, obtains graphene first product；The reduction
Agent is Nano-Zinc powder；
（3）By step（2）Obtained graphene first product is ground, and it is 10000 mesh to reach granularity；
（4）By the graphene first product and magnetism draw point abrasive body after grinding, it is put into closed grinding container, grinding is held
Device merging has in the tubular transformation magnetic field space formed to EDS maps, carries out stripping 48-58h, Nano graphite is made after stripping
The mixture dry powder of microplate-graphene；
（5）By step（4）The mixture dry powder of graphite nano micro-flake-graphene obtained detaches draw point, by sedimentation, from
After heart separation, the graphene transperent suspension liquid of high-purity is made.
As the priority scheme of the present invention, the metallic catalyst is zinc molybdate.
As the priority scheme of the present invention, the metal agent for capturing is diethylene triamine pentamethylene phosphonic.
As the priority scheme of the present invention, the step（4）The material of middle grinding container is austenitic stainless steel.
As the priority scheme of the present invention, the step（4）The conversion frequency of middle transformation magnetic field space is 2600-2800r/
Min, magnetic induction intensity 0.8-0.9T.
A kind of preparation process improving graphene purity of embodiment 1
A kind of preparation process improving graphene purity, includes the following steps：
（1）By metallic catalyst, metal agent for capturing and carbon materials, glucan, vinyl acetate-maleic anhydride copolymerization
Object, starch acrylonitrile graft copolymer, cellulose graft acrylonitrile hydrolysis product are stirred, and are adsorbed, are adsorbed with
The carbon source mixture of metallic catalyst；The metallic catalyst, metal agent for capturing and carbon materials, glucan, vinyl acetate-are suitable
Maleic anhydride copolymer, starch acrylonitrile graft copolymer, cellulose graft acrylonitrile hydrolysis product weight part ratio be 1：
0.5：1 ：0.2：0.6：0.2：0.4；
（2）By reducing agent and step（1）In be adsorbed with metallic catalyst carbon source mixture mixing after, according to heating speed
Rate is that be heated to temperature be 1000 DEG C to 13 DEG C/min, and constant temperature keeps 27h, obtains graphene first product；The reducing agent is Nano-Zinc
Powder；
（3）By step（2）Obtained graphene first product is ground, and it is 10000 mesh to reach granularity；
（4）By the graphene first product and magnetism draw point abrasive body after grinding, it is put into closed grinding container, grinding is held
Device merging has in the tubular transformation magnetic field space formed to EDS maps, carries out stripping 53h, it is micro- that Nano graphite is made after stripping
The mixture dry powder of piece-graphene；
（5）By step（4）The mixture dry powder of graphite nano micro-flake-graphene obtained detaches draw point, by sedimentation, from
After heart separation, the graphene transperent suspension liquid of high-purity is made.
As the priority scheme of the present invention, the metallic catalyst is zinc molybdate.
As the priority scheme of the present invention, the metal agent for capturing is diethylene triamine pentamethylene phosphonic.
As the priority scheme of the present invention, the step（4）The material of middle grinding container is austenitic stainless steel.
As the priority scheme of the present invention, the step（4）The conversion frequency of middle transformation magnetic field space is 2700r/min,
Magnetic induction intensity is 0.85T.
All above-mentioned this intellectual properties of primarily implementation, there is no this new products of implementation of setting limitation other forms
And/or new method.Those skilled in the art will utilize this important information, the above modification, to realize similar execution feelings
Condition.But all modifications or transformation belong to the right of reservation based on new product of the present invention.
Claims (6)
1. a kind of preparation process improving graphene purity, which is characterized in that include the following steps：
Step 1：By metallic catalyst, metal agent for capturing and carbon materials, glucan, vinyl acetate-maleic anhydride copolymerization
Object, starch acrylonitrile graft copolymer, cellulose graft acrylonitrile hydrolysis product are stirred, and are adsorbed, are adsorbed with
The carbon source mixture of metallic catalyst；The metallic catalyst, metal agent for capturing and carbon materials, glucan, vinyl acetate-are suitable
Maleic anhydride copolymer, starch acrylonitrile graft copolymer, cellulose graft acrylonitrile hydrolysis product weight part ratio be 1：
(0.4-0.6)：(0.8-1.2)：(0.1-0.3)：(0.5-0.7)：(0.1-0.3)：(0.3-0.5)；
Step 2：After reducing agent is mixed with the carbon source mixture for being adsorbed with metallic catalyst in step 1, according to heating rate
It is 950-1050 DEG C to be heated to temperature for 12-14 DEG C/min, and constant temperature keeps 26-28h, obtains graphene first product；The reducing agent
For Nano-Zinc powder；
Step 3：The graphene first product that step 2 obtains is ground, it is 10000 mesh to reach granularity；
Step 4：By the graphene first product and magnetism draw point abrasive body after grinding, it is put into closed grinding container, grinding is held
Device merging has in the tubular transformation magnetic field space formed to EDS maps, carries out stripping 48-58h, Nano graphite is made after stripping
The mixture dry powder of microplate-graphene；
Step 5：The mixture dry powder of graphite nano micro-flake-graphene made from step 4 is detached into draw point, by settling, centrifuging
After separation, the graphene transperent suspension liquid of high-purity is made.
2. a kind of preparation process improving graphene purity according to claim 1, which is characterized in that the metal catalytic
Agent is zinc molybdate.
3. a kind of preparation process improving graphene purity according to claim 1, which is characterized in that the metal captures
Agent is diethylene triamine pentamethylene phosphonic.
4. a kind of preparation process improving graphene purity according to claim 1, which is characterized in that in the step 4
The material of grinding container is austenitic stainless steel.
5. a kind of preparation process improving graphene purity according to claim 1, which is characterized in that in the step 4
The conversion frequency for converting magnetic field space is 2600-2800r/min, magnetic induction intensity 0.8-0.9T.
6. a kind of preparation process improving graphene purity according to claim 1, which is characterized in that including following step
Suddenly：
(1) by metallic catalyst, metal agent for capturing and carbon materials, glucan, vinyl acetate-maleic anhydride multipolymer,
Starch acrylonitrile graft copolymer, cellulose graft acrylonitrile hydrolysis product are stirred, and are adsorbed, obtain being adsorbed with metal
The carbon source mixture of catalyst；The metallic catalyst, metal agent for capturing and carbon materials, glucan, vinyl acetate-maleic
Anhydride multipolymer, starch acrylonitrile graft copolymer, cellulose graft acrylonitrile hydrolysis product weight part ratio be 1：0.5：
1：0.2：0.6：0.2：0.4；
(2) after mixing reducing agent with the carbon source mixture for being adsorbed with metallic catalyst in step (1), it is according to heating rate
It is 1000 DEG C that 13 DEG C/min, which is heated to temperature, and constant temperature keeps 27h, obtains graphene first product；The reducing agent is Nano-Zinc powder；
(3) the graphene first product that step (2) obtains is ground, it is 10000 mesh to reach granularity；
(4) it by the graphene first product and magnetism draw point abrasive body after grinding, is put into closed grinding container, grinding container is set
Enter in the tubular transformation magnetic field space for having and being formed to EDS maps, carries out stripping 53h, graphite nano micro-flake-stone is made after stripping
The mixture dry powder of black alkene；
The mixture dry powder of graphite nano micro-flake-graphene made from step (4) is detached into draw point, by settling, centrifuging
Afterwards, the graphene transperent suspension liquid of high-purity is made.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103935986A (en) * | 2014-02-28 | 2014-07-23 | 中国科学院宁波材料技术与工程研究所 | Method for high yield preparation of graphene by using biologic carbon source material |
| CN104556001A (en) * | 2014-12-19 | 2015-04-29 | 林前锋 | Method for preparing high-purity graphene |
| CN104876217A (en) * | 2015-06-01 | 2015-09-02 | 北京理工大学 | Graphene preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103935986A (en) * | 2014-02-28 | 2014-07-23 | 中国科学院宁波材料技术与工程研究所 | Method for high yield preparation of graphene by using biologic carbon source material |
| CN103935986B (en) * | 2014-02-28 | 2016-03-30 | 中国科学院宁波材料技术与工程研究所 | A kind of method preparing Graphene with biological carbon source material high yield |
| CN104556001A (en) * | 2014-12-19 | 2015-04-29 | 林前锋 | Method for preparing high-purity graphene |
| CN104876217A (en) * | 2015-06-01 | 2015-09-02 | 北京理工大学 | Graphene preparation method |
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