CN105502357B - A kind of mechanical stripping prepares the special remover of Graphene and preparation method - Google Patents
A kind of mechanical stripping prepares the special remover of Graphene and preparation method Download PDFInfo
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- CN105502357B CN105502357B CN201510965632.6A CN201510965632A CN105502357B CN 105502357 B CN105502357 B CN 105502357B CN 201510965632 A CN201510965632 A CN 201510965632A CN 105502357 B CN105502357 B CN 105502357B
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- C01B2204/00—Structure or properties of graphene
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Abstract
The special remover of Graphene and preparation method are prepared the invention discloses a kind of mechanical stripping, including：The composite nano particle of percentage by weight 25 ~ 35%, 1 ~ 5% dispersant and 60 ~ 74% deionized water, wherein, the composite nano particle is main body by metal or metal oxide nano powder, graphene oxide is surrounded by, the structure of grafted amino group group is constituted on graphene oxide.A kind of graphite layers that can effectively expand be this method provide away from contamination-freely peeling off graphite, additionally it is possible to which the mechanical stripping for preventing Graphene from reuniting prepares the special remover of Graphene.
Description
Technical field
The present invention relates to technical field of nanometer material preparation, more particularly to a kind of special remover of mechanical stripping Graphene and
Its preparation method.
Background technology
Graphene is the Two-dimensional Carbon atomic crystal for finding in recent years, is the research in current carbonaceous material and Condensed Matter Physics field
One of focus.Graphene is to construct the sp such as zero dimension fullerene, one-dimensional CNT, three-dimensional body phase graphite2The basic knot of hydridization carbon
Structure unit.It is also that oneself knows most thin one kind in material although Graphene only one of which carbon atom thickness, but Graphene is very
Rigid.Additionally, carbon atom has four valence electrons, so each carbon atom can contribute a pi-electron for non-bonding, this
A little pi-electrons can form π tracks with plane into vertical direction, and pi-electron can then be moved freely in crystal, assign Graphene good
Electric conductivity.These excellent characteristics make Graphene possess very vast potential for future development.
In order to allow outstanding grapheme material to realize industrialized production and application, must just develop one kind can give birth on a large scale
Produce and the number of plies and the controllable preparation method of size.The preparation method of current Graphene has mechanical stripping method, epitaxial growth method, oxidation
Reducing process, ultrasonic stripping method, organic synthesis method, solvent-thermal method, chemical vapour deposition technique etc..In these methods, due to machinery
Stripping method can most preferably preserve the property of Graphene, and preparation method is simple, and preparation process is environment friendly and pollution-free, in reality
Favor is enjoyed in production.
China Patent Publication No. 102874797A discloses a kind of extensive method for preparing high-quality graphene, the method
Expanded graphite is scattered in stripper solution and stirs dipping, through filtering, washing dries prepared Graphene.The present invention has system
Standby mild condition, simple to operate, the advantage easily accomplished scale production.But, the method is due to using ultrasonic immersing stripping
Graphite after agent, to graphite and the finite energy for peeling off immunomodulator compounds system, therefore, open the general of graphite layers Van der Waals force
Rate is very low, so that, the yield of Graphene is very low.
China Patent Publication No. 102701187A discloses a kind of preparation method of Graphene and uses the method preparation
Graphene.The invention is obtained compound between graphite layers with graphite as raw material by inserting metal in graphite layers, then peels off
The compound between graphite layers and be obtained Graphene.The method is by the use of metal as remover, preparation method is simple, low cost
It is honest and clean.But, the method metal in the stripping process enters after graphite layers, and metal is in graphite layers accumulative crystallization, or shape
During carbide, metallic atom is direction-free to grow up, and causes graphene sheet layer to be pierced, and reduces the chi of Graphene
It is very little, the two-dimensional physical structure of graphite flake layer is destroyed, its mechanical performance and electric conductivity is deteriorated.
China Patent Publication No. 103935999A discloses a kind of preparation method of Graphene.The method is with polar solvent
Decentralized medium, is by mechanically pulling off method and prepares high-quality graphene, mainly using Graphene under graphene quantum dot auxiliary
The good dispersiveness in polar solvent of quantum dot, and its stronger non-covalent bond between Graphene/graphene sheet layer is combined,
Promote the dispersion of the stripping and graphene nanometer sheet of native graphite in polar solvent, so as to obtain high-quality Graphene.Should
Method is simple to operate, but the Graphene for obtaining is tightly combined with remover or dispersant, it is difficult to purifying and transfer.
In sum, existing mechanical stripping method also i.e. can be not effectively without one kind in preparing the technology of Graphene now
Expand graphite layers away from contamination-freely peeling off graphite, additionally it is possible to which it is special that the mechanical stripping for preventing Graphene from reuniting prepares Graphene
Remover.
The content of the invention
In order to solve the deficiency and defect of the above method, the present invention develops a kind of mechanical stripping and prepares the special stripping of Graphene
From agent.The method uses the nanoparticle of the graphene oxide parcel of grafted amino group acid as the main body of remover, using oxidation
The π keys that Graphene has form π-π effects with Graphene, and using the sharpened surface of nanoparticle, insertion graphite layers peel off stone
Black alkene, the amino group protonation using graft product makes Graphene powered, and the reunion of Graphene is prevented by Coulomb repulsion.
On the one hand, the present invention provides a kind of mechanical stripping and prepares the special remover of Graphene, it is characterised in that the stripping
Consisted of the following composition from agent, including：The composite nano particle of the % of percentage by weight 25 ~ 35, the dispersant of 1 ~ 5 % and 60 ~ 74
The deionized water of %；
Wherein, the composite nano particle is main body by metal or metal oxide nano powder, is surrounded by oxidation stone
Black alkene, the structure of grafted amino group group is constituted on graphene oxide.
Preferably, the metal or metal oxide nano powder diameter of particle are 20 ~ 50nm, the piece of the graphene oxide
Footpath is 100-300nm.
Preferably, the metal or metal oxide nanoparticles and graphene oxide mass ratio are 2 ~ 8: 1.
Preferably, the metal or metal oxide nano powder are nanometer iron powder, and copper nanoparticle, Nano-sized Ferric Oxide Powder is received
Rice cupric oxide powder, one or more in nano alumina powder；The amino group derives from leucine, isoleucine, egg ammonia
One kind in acid, aspartic acid, glutamic acid, lysine, arginine, glycine, serine, threonine, alanine, phenylalanine
Or it is several.
Preferably, the dispersant is in lauryl sodium sulfate, dodecyl sodium sulfate and polyvinylpyrrolidone
One or more.
On the other hand, the present invention provides the preparation method that a kind of mechanical stripping prepares the special remover of Graphene, its feature
It is to comprise the following steps:
Metal or metal oxide nanoparticles are blended with graphene oxide, deionized water and dispersant is added, with stirring
The machine of mixing stirs, and is heated to 50 ~ 80 DEG C, obtains turbid solution；
During amino acid added into previous step turbid solution, it is kept stirring for 3 ~ 5 hours, using esterification by amino group graft
In the surface of graphene oxide, temperature to room temperature is reduced, obtain remover.
Preferably, the mixer mixing speed is 40 ~ 80 revs/min.
Said one or multiple technical schemes in the embodiment of the present application, at least imitate with following one or more technology
Really：
1st, this kind of remover has protective effect during Graphene is peeled off to Graphene, it is to avoid Graphene itself
The increase of defect.And, to a certain extent, the Graphene to peeling off has repair.
2nd, in this kind of remover, the amino group protonation of graft product makes Graphene powered, is prevented by Coulomb repulsion
The reunion of Graphene, the smooth Graphene of readily available high-quality.
3rd, this kind of remover, due to containing metal or metal oxide microparticle in nanoparticle, relative density increases, is easy to
The centrifugation in later stage, reduces the impurity in graphene product.
Specific embodiment
By specific embodiment, the present invention is described in further detail, but this should not be interpreted as into model of the invention
Enclose and be only limitted to following example.In the case where above method thought of the present invention is not departed from, according to ordinary skill knowledge
The various replacements or change made with customary means, should be included in the scope of the present invention.
Embodiment one
The composition of remover is as follows in the present embodiment：
Composite nano particle, percentage by weight is 25%；Lauryl sodium sulfate, percentage by weight is 2%；And deionization
Water, percentage by weight is 73%.
Remover is prepared from by following step：
Metal iron nanoparticle of the particle diameter for 20nm is chosen with piece footpath for the graphene oxide of 100nm mixes, metallic iron is received
Rice particulate is 2 with graphene oxide mass ratio:1, add appropriate dispersant lauryl sodium sulfate and appropriate deionization
Water, is stirred with mixer, and the mixing speed for setting mixer is 40 revs/min, is heated to 50 DEG C, obtains turbid solution.Will
The leucine of the metering of graphene oxide 1/3 is added in above-mentioned turbid solution, stands 12h, after reaction to be esterified terminates, reduces temperature extremely
Room temperature, and then obtain containing based on metallic iron nanometer powder, metallic iron nano-powder outside parcel graphene oxide is aoxidized
The solvent of the composite nano particle of grafted amino group group prepares the special remover of Graphene for mechanical stripping on Graphene.
The remover prepared in Example one is 1 with expanded graphite mass ratio：50, the size of the Graphene for preparing
It is 2.09 μm（Selected area size）, thickness is 0.83 nm, and yield is 11.5%.
Embodiment two
Composite nano particle, percentage by weight is 25%；Lauryl sodium sulfate, percentage by weight is 2%；And deionization
Water, percentage by weight is 73%.
Remover is prepared from by following step：
Metal iron nanoparticle of the particle diameter for 40nm is chosen with piece footpath for the graphene oxide of 300nm mixes, metallic iron is received
Rice particulate is 4 with graphene oxide mass ratio:1, add appropriate dispersant lauryl sodium sulfate and appropriate deionization
Water, is stirred with mixer, and the mixing speed for setting mixer is 40 revs/min, is heated to 50 DEG C, obtains turbid solution.Will
The leucine of the metering of graphene oxide 1/3 is added in above-mentioned turbid solution, stands 12h, after reaction to be esterified terminates, reduces temperature extremely
Room temperature, and then obtain containing based on metallic iron nanometer powder, metallic iron nano-powder outside parcel graphene oxide is aoxidized
The solvent of the composite nano particle of grafted amino group group prepares the special remover of Graphene for mechanical stripping on Graphene.
The remover prepared in Example two is 1 with expanded graphite mass ratio：50, the size of the Graphene for preparing
It is 3.23 μm（Selected area size）, thickness is 0.82 nm, and yield is 10.7%.
Embodiment three
Composite nano particle, percentage by weight is 35%；Dodecyl sodium sulfate, percentage by weight is 1%；And deionization
Water, percentage by weight is 64%.
Remover is prepared from by following step：
Metal iron nanoparticle of the particle diameter for 40nm is chosen with piece footpath for the graphene oxide of 300nm mixes, metallic iron is received
Rice particulate is 4 with graphene oxide mass ratio:1, add appropriate dispersant lauryl sodium sulfate and appropriate deionization
Water, is stirred with mixer, and the mixing speed for setting mixer is 40 revs/min, is heated to 50 DEG C, obtains turbid solution.Will
The leucine of the metering of graphene oxide 1/3 is added in above-mentioned turbid solution, stands 12h, after reaction to be esterified terminates, reduces temperature extremely
Room temperature, and then obtain containing based on metallic iron nanometer powder, metallic iron nano-powder outside parcel graphene oxide is aoxidized
The solvent of the composite nano particle of grafted amino group group prepares the special remover of Graphene for mechanical stripping on Graphene.
The remover prepared in Example three is 1 with expanded graphite mass ratio：50, the size of the Graphene for preparing
It is 2.09 μm（Selected area size）, thickness is 0.83 nm, and yield is 17.5%.
Example IV
Composite nano particle, percentage by weight is 35%；Dodecyl sodium sulfate, percentage by weight is 1%；And deionization
Water, percentage by weight is 64%.
Remover is prepared from by following step：
Nano alumina particles of the particle diameter for 40nm are chosen with piece footpath for the graphene oxide of 300nm mixes, it is nano oxidized
Aluminium particulate is 4 with graphene oxide mass ratio:1, add appropriate dispersant lauryl sodium sulfate and appropriate deionization
Water, is stirred with mixer, and the mixing speed for setting mixer is 40 revs/min, is heated to 50 DEG C, obtains turbid solution.Will
The alanine of the metering of graphene oxide 1/3 is added in above-mentioned turbid solution, stands 12h, after reaction to be esterified terminates, reduces temperature extremely
Room temperature, and then obtain containing based on metallic iron nanometer powder, graphene oxide, graphite oxide are wrapped up in nano aluminium oxide outside
The solvent of the composite nano particle of grafted amino group group prepares the special remover of Graphene for mechanical stripping on alkene.
The remover prepared in Example four is 1 with expanded graphite mass ratio：50, the size of the Graphene for preparing
It is 4.01 μm（Selected area size）, thickness is 0.97 nm, and yield is 17.2%.
Embodiment five
Composite nano particle, percentage by weight is 35%；Dodecyl sodium sulfate, percentage by weight is 1%；And deionization
Water, percentage by weight is 64%.
Remover is prepared from by following step：
Nano alumina particles of the particle diameter for 50nm are chosen with piece footpath for the graphene oxide of 300nm mixes, it is nano oxidized
Aluminium particulate is 8 with graphene oxide mass ratio:1, add appropriate dispersant lauryl sodium sulfate and appropriate deionization
Water, is stirred with mixer, and the mixing speed for setting mixer is 80 revs/min, is heated to 80 DEG C, obtains turbid solution.Will
1/4 mole of serine of metering of graphene oxide is added in above-mentioned turbid solution, stands 12h, after reaction to be esterified terminates, reduces temperature
Degree is obtained containing based on metallic iron nanometer powder to room temperature, and graphene oxide, oxidation are wrapped up in nano aluminium oxide outside
The solvent of the composite nano particle of grafted amino group group prepares the special remover of Graphene for mechanical stripping on Graphene.
The remover prepared in Example five is 1 with expanded graphite mass ratio：50, the size of the Graphene for preparing
It is 1.59 μm（Selected area size）, thickness is 0.77 nm, and yield is 15.3%
, but those skilled in the art once know basic creation although preferred embodiments of the present invention have been described
Property concept, then can make other change and modification to these embodiments.So, appended claims are intended to be construed to include excellent
Select embodiment and fall into having altered and changing for the scope of the invention.
Obviously, those skilled in the art can carry out various changes and modification without deviating from essence of the invention to the present invention
God and scope.So, if these modifications of the invention and modification belong to the scope of the claims in the present invention and its equivalent technologies
Within, then the present invention is also intended to comprising these changes and modification.
Claims (7)
1. a kind of mechanical stripping prepares the special remover of Graphene, it is characterised in that the remover is consisted of the following composition：Weight
The deionized water of the composite nano particle of amount percentage 25 ~ 35 %, the dispersant of 1 ~ 5 % and 60 ~ 74 %；
Wherein, the composite nano particle is main body by metal or metal oxide nano powder, is surrounded by graphene oxide,
The structure of grafted amino group group is constituted on graphene oxide.
2. a kind of mechanical stripping according to claim 1 prepares the special remover of Graphene, it is characterised in that the metal
Or metal oxide nano powder diameter of particle is 20 ~ 50nm, the piece footpath of the graphene oxide is 100-300nm.
3. a kind of mechanical stripping according to claim 1 prepares the special remover of Graphene, it is characterised in that the metal
Or metal oxide nano powder and graphene oxide mass ratio are 2 ~ 8: 1.
4. a kind of mechanical stripping according to claim 1 prepares the special remover of Graphene, it is characterised in that the metal
Or metal oxide nano powder is nanometer iron powder, copper nanoparticle, Nano-sized Ferric Oxide Powder, nano oxidized copper powder, nano alumina powder
In one or more；The amino group is from leucine, isoleucine, methionine, aspartic acid, glutamic acid, bad ammonia
One or more in acid, arginine, glycine, serine, threonine, alanine, phenylalanine.
5. a kind of mechanical stripping according to claim 1 prepares the special remover of Graphene, it is characterised in that the dispersion
Agent is one or more in lauryl sodium sulfate, dodecyl sodium sulfate and polyvinylpyrrolidone.
6. a kind of mechanical stripping described in a kind of claim 1 prepares the preparation method of the special remover of Graphene, and its feature exists
In comprising the following steps:
A. metal or metal oxide nano powder are blended with graphene oxide, add deionized water and dispersant, use mixer
Stir, be heated to 50 ~ 80 DEG C, obtain turbid solution；
B. amino acid is added in the turbid solution of a steps, is kept stirring for 3 ~ 5 hours, using esterification by amino group graft
In the surface of graphene oxide, temperature to room temperature is reduced, obtain remover.
7. a kind of mechanical stripping according to claim 6 prepares the preparation method of the special remover of Graphene, and its feature exists
In the mixer mixing speed is 40 ~ 80 revs/min.
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| CN106517166B (en) * | 2016-10-19 | 2018-05-18 | 成都新柯力化工科技有限公司 | A kind of compound remover that graphene is prepared for slurry stirring stripping |
| CN106744870B (en) * | 2016-10-25 | 2019-01-04 | 成都新柯力化工科技有限公司 | A kind of abrasive media grinding removing graphene for slurry |
| CN107857260B (en) * | 2017-12-13 | 2020-02-07 | 西北有色金属研究院 | Method for preparing graphene oxide through weak oxidation intercalation stripping |
| CN107936159A (en) * | 2017-12-22 | 2018-04-20 | 安徽工业大学 | A kind of preparation method of the high quick selfreparing physical hydrogel of stretching |
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| CN102701187B (en) * | 2011-07-13 | 2016-03-09 | 华东理工大学 | Graphene prepared by a kind of preparation method of Graphene and use the method |
| CN102874797A (en) * | 2012-09-17 | 2013-01-16 | 中国科学院山西煤炭化学研究所 | Method for massively preparing high-quality graphene |
| CN104973591B (en) * | 2014-04-11 | 2017-02-08 | 中国科学院上海硅酸盐研究所 | High-quality graphene and preparation method thereof |
| CN104030283B (en) * | 2014-06-30 | 2016-06-01 | 上海交通大学 | A kind of method obtaining two-dimensional material based on graphene quantum dot stripping |
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