CN106517166B - A kind of compound remover that graphene is prepared for slurry stirring stripping - Google Patents
A kind of compound remover that graphene is prepared for slurry stirring stripping Download PDFInfo
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- CN106517166B CN106517166B CN201610909609.XA CN201610909609A CN106517166B CN 106517166 B CN106517166 B CN 106517166B CN 201610909609 A CN201610909609 A CN 201610909609A CN 106517166 B CN106517166 B CN 106517166B
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Abstract
The present invention provides a kind of compound remover that graphene is prepared for slurry stirring stripping, and the compound remover is made of surfactant, organic solvent, ionic liquid, protonating agent, hydrated salt and softened water.The compound remover has graphite prominent permeability and dilatancy, and using the compound remover of the graphene, graphite is more easily peelable during removing into graphene, it is only necessary to can be realized by simple mixing plant.Simpler so as to fulfill the preparation process of graphene, energy consumption reduces, while graphene film layer structure can also be protected not to be destroyed, and is more suitable for the industrialization large-scale production of high-quality graphene.
Description
Technical field
The present invention relates to technical field of graphene preparation, and graphene is prepared for slurry stirring stripping more particularly to one kind
Compound remover.
Background technology
Due to the two-dimentional monoatomic layer crystal structure of graphene uniqueness so that it have excellent optics, mechanics, electricity and
The performances such as calorifics, so as to be widely used in the fields such as composite material, energy storage device electronic device and pollution control.At present, it is traditional
Preparation method constrain its application and development, thus the exploration of novel processing step is extremely urgent.
The preparation method of graphene includes Physical and chemical method, and Physical mainly has mechanical stripping method, heating carborundum
Method, epitaxy method etc., chemical method mainly have the chemical vapor precipitation method, graphite oxide reduction method etc..
Mechanical stripping method is to be removed graphite flake layer by layer using mechanical force, so as to obtain single-layer graphene.
Traditional mechanical stripping method is " tear tape " method, and highly oriented pyrolytic graphite is constantly removed repeatedly by adhesive tape by Geim seminar,
Then obtained sample is transferred on silicon chip, finally falls adhesive tape with acetone solution, be prepared into single-layer graphene for the first time.This side
Method is simple, but it is graphene to be difficult to realize prepare on a large scale, and size is not easily controlled.
Heating carbonization silicon process is by heating monocrystalline silicon carbide, under the high temperature conditions, the Si on surface is etched away so that carbon
Atom precipitation reconfigures to form graphene, and the graphene quality that this method is prepared is higher.But its obtained graphene
It is individual layer and the mixture of multilayer mostly, and is not easy to shift there are stronger effect with matrix so that this method is not easy scale
Metaplasia is produced.
Epitaxy method is again that one layer of single crystalline layer identical with Substrate orientation is grown in single crystalline substrate.
The chemical vapor precipitation method are the methods that a kind of most widely used heavy industrialization prepares semiconductor film material,
And a research direction of graphene is prepared at present.This method mainly decomposed at high temperature using gaseous carbon source after in matrix table
Graphene is prepared in catalytic growth on face, and this method is to prepare the important method of high quality and large area single-layer graphene.
But technique is also immature at this stage for this method, production cost all limits its large-scale application.
Electronation graphene oxide method is fully to be removed graphite oxide in water, then carries out electronation to it
Or thermal reduction obtains graphene, this method can prepare a large amount of grapheme materials, and cost is relatively low, can be applied to antistatic painting
Layer, flexible and transparent electronic equipment, high-performance are set up and nanosecond medical science field, but there is also defect, due to by Strong oxdiative-also
Former process, the electron conjugated structure of graphene sheet layer are destroyed, and cause it that can lose some physical and chemical performances.And graphite
Oxidation process in need high-temperature process or using hydrazine hydrate, the toxic chemical substance such as sodium borohydride, not only energy consumption it is big,
Efficiency is low, of high cost, and pollutes environment.
The simple process and low cost of mechanical stripping method, pollution-free, domestic and international many scholars are in research and utilization mechanical stripping
Method produces graphene.The maximum feature that Mechanical Method prepares graphene is exactly not carry out oxidation work to graphite in stripping process
With, therefore the graphene of high quality can be obtained.But mechanical stripping method low output of the prior art, is only applicable to basic section
It grinds, be but difficult to realize mass produce and industrialize continuous preparation.
In addition, there are stronger model ylid bloom action power each other to prevent it from stable dispersion in a solvent for graphene, with it
His compatibility of material is also bad, easily stacked together again to be difficult to open, this is one of restriction graphene application main
Obstacle.
To sum up, a kind of efficient graphene remover how is provided, graphene is extensive, high quality, low cost to solve
Preparation, be research graphene prepare and using urgent problem to be solved.
The content of the invention
The purpose of invention is overcome in existing graphene preparation process, is also needed to using traditional graphene remover auxiliary
The ancillary equipments such as mechanical stripping, ultrasound stripping are helped, preparation process is more demanding to mechanical equipment, and energy consumption is also higher, and carries
For a kind of compound remover that graphene is prepared for slurry stirring stripping.The compound remover there is protrusion to ooze graphite
Permeability and dilatancy, using the compound remover of the graphene, graphite is more easily peelable during removing into graphene, only
It need to be can be realized by simple mixing plant.
The compound remover of graphene using the present invention, the preparation process of graphene is simpler, and energy consumption reduces, simultaneously
Graphene film layer structure can also be protected not to be destroyed, be more suitable for the industrialization large-scale production of high-quality graphene.
The weight percent of the compound remover of graphene of the present invention, component and each component is as follows：
Hydrated salt 10%-20%,
Surfactant 12%-15%,
Organic solvent 30-40%,
Ionic liquid 5%-15%,
Protonating agent 2%-5%,
Surplus is softened water；
Wherein, the hydrated salt is at least one of sodium tetraborate, sodium metasilicate, sodium phosphate；
The surfactant is in alkylbenzenesulfonate, alkyl bromination ammonium, alkyl glycosides and fatty alcohol Polyoxyalkylene ethers
One or more；
The organic solvent is at least one of sulfoxide, sulfone；
The ionic liquid is glyoxaline ion liquid；
The protonating agent is at least one of benzoic acid, 2- naphthoic acids, 1- pyrenes formic acid, 1- pyrene sulfonic acid；
Preferably, the hydrated salt weight percent is 15%.
Preferably, the alkylbenzenesulfonate be neopelex, cetyl benzenesulfonic acid sodium, detergent alkylate
One or more in potassium sulfonate；The alkyl bromination ammonium be cetyl ammonium bromide, cetyl trimethylammonium bromide, 14
Alkyl trimethyl ammonium bromide, the one or more in dodecyl trimethyl ammonium bromide；The alkyl glycosides is dodecyl wheat
Bud glucosides, the one or more in lauryl glucosyl；The fatty alcohol polyoxyethylene ether is ethoxylated dodecyl alcohol,
Polyoxyethylene octadecanol, the one or more in hexadecanol polyoxyethylene ether.
It is further preferred that the surfactant is pressed for cetyl trimethylammonium bromide and neopelex
1:The mass ratio mixing of 0.25-0.5.
Preferably, the sulfoxide is the one or more in dimethyl sulfoxide (DMSO), diethyl sulfoxide and first ethyl-sulfoxide；Institute
The sulfone stated is the one or more in methyl sulfone, ethyl sulfone and sulfolane.
The ionic liquid is chlorination 1- octyl group -3- methylimidazole salts, chlorination 1- butyl -3- methyl miaows
Azoles salt, double (trifluoromethyl sulfonyl) inferior amine salts of 1- butyl -3- methylimidazoles, 1- hexyl -3- methylimidazoles
One or more in hexafluorophosphate.
Further preferably, the ionic liquid is chlorination 1- octyl group -3- methylimidazole salts.
On the other hand, the ionic liquid for chlorination 1- octyl group -3- methylimidazole salts, chlorination 1- butyl -
3- methylimidazole salts and double (trifluoromethyl sulfonyl) inferior amine salts of 1- butyl -3- methylimidazoles press 1:1-2:1-2's
Mass ratio mixes.
Preferably, the protonating agent presses 1 for benzoic acid and 1- pyrenes formic acid:The mass ratio mixing of 1-2.
The positive effect of the present invention is：
（1）A kind of compound remover that graphene is prepared for slurry stirring stripping is provided.By special hydrated salt with from
Sub- liquid, protonating agent etc. constitute permeability and expansile compound remover with protrusion, and graphite is being removed into graphene
During it is more easily peelable, it is only necessary to can be realized by simple mixing plant.
（2）The compound remover of graphene using the present invention, the preparation process of graphene is simpler, and energy consumption reduces
（3）Graphene film layer structure can be protected not to be destroyed, tradition machinery stripping is overcome and graphene layer lattice is rushed
It hits, available for the graphene for preparing high quality.
It is of the present invention graphene is prepared for slurry stirring stripping compound remover it is simple for production, each formula by
Raw material are uniformly mixed through simple.
Application method of the present invention for the slurry stirring stripping compound remover for preparing graphene is：By graphite
Powder is added in stirred tank, and adding in water disperses graphite powder, stirs, speed of agitator 5000-15000r/min, then adds in this
The invention compound remover of graphene continues stirring and removes, obtains graphene slurries.
Specific embodiment
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Scope be only limitted to following example.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
Exemplified by preparing the compound removers of 100kg, one kind described in the present embodiment prepares graphite for slurry stirring stripping
The compound stripping agent prescription of alkene, including：It is sodium tetraborate 10kg, sodium metasilicate 5kg wherein to close salt；Neopelex
12kg；Diethyl sulfoxide 20kg, first ethyl-sulfoxide 10kg；Chlorination 1- butyl -3- methylimidazole salts 10kg；Benzoic acid 2kg；
Softened water 31kg.
Embodiment 2
Exemplified by preparing the compound removers of 100kg, one kind described in the present embodiment prepares graphite for slurry stirring stripping
The compound stripping agent prescription of alkene, including：Sodium phosphate 20kg；Lauryl glucosyl 15kg；Ethyl sulfone 30kg；1- hexyls-
3- methylimidazole hexafluorophosphates 15kg；2- naphthoic acids 5kg；Softened water 15kg.
Embodiment 3
Exemplified by preparing the compound removers of 100kg, one kind described in the present embodiment prepares graphite for slurry stirring stripping
The compound stripping agent prescription of alkene, including：Sodium metasilicate 5kg, sodium phosphate 15kg；Polyoxyethylene octadecanol 10kg, hexadecanol gather
Ethylene oxide ether 2kg；Diethyl sulfoxide 30kg；Double (trifluoromethyl sulfonyl) inferior amine salts of 1- butyl -3- methylimidazoles
10kg；1- pyrene formic acid 5kg；Softened water 23kg.
Embodiment 4
Exemplified by preparing the compound removers of 100kg, one kind described in the present embodiment prepares graphite for slurry stirring stripping
The compound stripping agent prescription of alkene, including：Sodium metasilicate 20kg；Cetyl ammonium bromide 12kg；Methyl sulfone 35kg；Chlorination 1- fourths
Base -3- methylimidazole salts 5kg；At least one of 1- pyrene sulfonic acid 3kg；Softened water 25kg.
Embodiment 5
Exemplified by preparing the compound removers of 100kg, one kind described in the present embodiment prepares graphite for slurry stirring stripping
The compound stripping agent prescription of alkene, including：It is sodium tetraborate 15kg wherein to close salt；Lauryl.beta.-maltoside 15kg；Sulfolane
40kg；Chlorination 1- octyl group -3- methylimidazole salts 5kg；2- naphthoic acids 5kg；Softened water 20kg.
It is specifically used
The compound remover that embodiment 1-5 is obtained prepares graphene for slurry stirring stripping, and application method is：It will
100g graphite powders are added in stirred tank, and adding in water 500g disperses graphite powder, stirs, speed of agitator 5000-8000r/
Min then adds in the compound remover 100g of graphene of the present invention, continue stirring remove 8 it is small when, obtain graphene slurry
Liquid.
Measure graphene content
Above-mentioned graphene slurry and blank sample are taken respectively（Not plus compound remover, 100g water is added in）It is compared, is used
UV-vis measures the absorbance of gained graphene slurry, then calculates and acquire its graphene concentration.Test result such as table 1：
Table 1：
The result shows that being obviously improved using the peeling effect of compound stripper of the present invention, graphene yield is more than
50%.Further, the peeling effect obtained is also not only that various raw materials obtain the simple superposition of result.
Claims (8)
1. a kind of compound remover that graphene is prepared for slurry stirring stripping, it is characterised in that：Its component and each component
Weight percent is as follows：
Hydrated salt 10%-20%,
Surfactant 12%-15%,
Organic solvent 30-40%,
Ionic liquid 5%-15%,
Protonating agent 2%-5%,
Surplus is softened water；
Wherein, the hydrated salt is at least one of sodium tetraborate, sodium metasilicate, sodium phosphate；
The surfactant is in alkylbenzenesulfonate, alkyl bromination ammonium, alkyl glycosides and fatty alcohol polyoxyethylene ether
It is one or more kinds of；
The organic solvent is at least one of sulfoxide, sulfone；
The ionic liquid is glyoxaline ion liquid；
The protonating agent is at least one of benzoic acid, 2- naphthoic acids, 1- pyrenes formic acid, 1- pyrene sulfonic acid.
2. a kind of compound remover that graphene is prepared for slurry stirring stripping according to claim 1, it is characterised in that：
The hydrated salt weight percent is 15%.
3. a kind of compound remover that graphene is prepared for slurry stirring stripping according to claim 1, it is characterised in that：
The alkylbenzenesulfonate is neopelex, cetyl benzenesulfonic acid sodium, one kind in Potassium dodecylbenzenesulfonate
It is or a variety of；The alkyl bromination ammonium be cetyl ammonium bromide, cetyl trimethylammonium bromide, tetradecyltrimethylammonium bromination
Ammonium, the one or more in dodecyl trimethyl ammonium bromide；The alkyl glycosides be Lauryl.beta.-maltoside, dodecyl
One or more in glucoside；The fatty alcohol polyoxyethylene ether be ethoxylated dodecyl alcohol, octodecyl alcohol polyoxyethylene
Ether, the one or more in hexadecanol polyoxyethylene ether.
4. a kind of compound remover that graphene is prepared for slurry stirring stripping according to claim 1, it is characterised in that：
The surfactant presses 1 for cetyl trimethylammonium bromide and neopelex:The mass ratio of 0.25-0.5 mixes
It closes.
5. a kind of compound remover that graphene is prepared for slurry stirring stripping according to claim 1, it is characterised in that：
The sulfoxide is the one or more in dimethyl sulfoxide (DMSO), diethyl sulfoxide and first ethyl-sulfoxide；The sulfone for methyl sulfone,
One or more in ethyl sulfone and sulfolane.
6. a kind of compound remover that graphene is prepared for slurry stirring stripping according to claim 1, it is characterised in that：
The ionic liquid be chlorination 1- octyl group -3- methylimidazole salts, chlorination 1- butyl -3- methylimidazole salts, 1- fourths
Double (trifluoromethyl sulfonyl) inferior amine salts of base -3- methylimidazoles, in 1- hexyl -3- methylimidazole hexafluorophosphates
One or more.
7. a kind of compound remover that graphene is prepared for slurry stirring stripping according to claim 1, it is characterised in that：
The ionic liquid is chlorination 1- octyl group -3- methylimidazole salts, chlorination 1- butyl -3- methylimidazole salts and 1- fourths
Double (trifluoromethyl sulfonyl) inferior amine salts of base -3- methylimidazoles press 1:1-2:The mass ratio mixing of 1-2.
8. a kind of compound remover that graphene is prepared for slurry stirring stripping according to claim 1, it is characterised in that：
The protonating agent presses 1 for benzoic acid and 1- pyrenes formic acid:The mass ratio mixing of 1-2.
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| CN106564887B (en) * | 2016-11-01 | 2018-12-28 | 日照鲁光电子科技有限公司 | A kind of graphene semiconductor composite material and preparation method |
| CN110642547B (en) * | 2019-10-25 | 2022-05-27 | 菲大装配式建筑工程(重庆)有限责任公司 | Graphene slurry and graphene aerated concrete |
| CN115367743B (en) * | 2022-09-05 | 2024-02-09 | 合肥艾克思维新材料科技有限公司 | Graphene stripping agent, preparation method of graphene, graphene modified rubber and preparation method of graphene modified rubber |
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| CN103253659B (en) * | 2013-05-23 | 2015-09-23 | 渤海大学 | A kind of ultrasonic wave peels off the method for preparing graphite alkene |
| CN103570012B (en) * | 2013-10-29 | 2016-04-27 | 安徽百特新材料科技有限公司 | A kind of preparation method of Graphene |
| CN105502357B (en) * | 2015-12-22 | 2017-05-31 | 成都新柯力化工科技有限公司 | A kind of mechanical stripping prepares the special remover of Graphene and preparation method |
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