CN104860311B - Preparation method of graphene - Google Patents
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- CN104860311B CN104860311B CN201510274571.9A CN201510274571A CN104860311B CN 104860311 B CN104860311 B CN 104860311B CN 201510274571 A CN201510274571 A CN 201510274571A CN 104860311 B CN104860311 B CN 104860311B
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Abstract
The invention belongs to the technical field of graphene preparation, and particularly relates to a preparation method of graphene. The preparation method comprises the following steps: adding a carbon material containing a graphite sheet structure, a reaction solution containing a graphite intercalation or/and peeling function components, a surface active agent and a power source substance into a reactor, and uniformly mixing to obtain reaction slurry; then performing peeling reaction to prepare graphene slurry, wherein in the peeling process of graphite sheets, the surface active agent can quickly wrap the peeled graphite sheets to prevent the graphite sheets from being re-stacked; finally, performing separation and purification to obtain a graphene product. Compared with the prior art, the preparation method has the advantages that when the graphene is prepared by using the method, the problems of potential safety hazard and environmental pollution in the process of preparing the graphene through an oxidation-reduction method can be solved; meanwhile, the graphene with small sheet number can be prepared in a large-batch, low-cost and industrial manner.
Description
Technical field
The invention belongs to technical field of graphene, particularly to a kind of preparation method of Graphene.
Background technology
2004, peace moral strong k sea nurse (andre k.geim) of Univ Manchester UK etc. adopted mechanical stripping
Method prepares Graphene (graphene) first, has thus pulled open the preparation of this material, the prelude of operational research.So-called graphite
Alkene, refers to be in a kind of plates of hexagonal annular arrangement between carbon atom, is generally made up of single or multiple lift graphite flake layer, can be
Two-dimensional space infinitely extends it may be said that being proper two-dimensional structure material.It has, and specific surface area is big, electrical and thermal conductivity
Can excellent, the low outstanding advantages of thermal coefficient of expansion: specifically, high specific surface area (calculated value: 2630m2/g)；Height is led
Electrically, carrier transport rate (200000cm2/v·s)；High heat conductance (5000w/mk)；High intensity, high Young's modulus
(1100gpa), fracture strength (125gpa).Therefore it has pole in energy storage field, conduction of heat field and Materials with High Strength field
Big utilization prospect.
The existing method preparing Graphene mainly has micromechanics stripping method, ultrahigh vacuum Graphene epitaxial growth method, oxygen
Change-reducing process, chemical vapour deposition technique (cvd), solvent stripping method, electrolysis and solvent-thermal method.In this serial of methods, oxygen
Change-reducing process and electrolysis are to realize the preferred version that Graphene is prepared on a large scale.
However, when preparing graphite oxide using oxidizing process, the oxidant being used is often the oxygen such as concentrated sulphuric acid, potassium permanganate
Agent；And in order to more fully by graphite oxidation, generally require to carry out pyroreaction.Exist greatly therefore in preparation process
Potential safety hazard, and oxidant Problem of Failure can occur, lead to whole oxidation reaction failure；Meanwhile, can produce in preparation process greatly
The waste liquid of amount, causes the increase of environmental pollution Manufacturing cost.
Comparatively speaking, when electrochemical method prepares Graphene, the reactant being used is typically electrolyte, and it is in operation
During potential safety hazard low, and environmental pollution is little.A kind of preparing graphene by electrochemical stripping as Sun Feng et al. invention
Method (application number cn 201110269176.3), use first graphitiferous material pole piece, containing lithium to electrode plates, contain carbonic acid
The electrolyte of propylene (pc) and barrier film are assembled into battery, make solvation Lithium-ion embeding graphite linings by discharging or charging
Between, final graphite peels off formation Graphene layer by layer.With respect to prior art, the present invention fully takes into account the incompatible of graphite and pc
Property and during discharge and recharge lithium ion can insert the feature in graphite layer by layer so that graphite is completely solvated lithium ion insertion layer by layer
And finally it is stripped generation Graphene.The method of this preparing graphene by electrochemical stripping without using the equipment of complex and expensive,
Simple to operate, and only need to carry out simple discharge and recharge and post processing can be obtained by Graphene.But electrode group is dressed up battery core
During, manufacturing cost is high, and the control due to electrode applied thickness, and the Graphene product amount obtaining is few, work difficult to realize
Industry is prepared on a large scale；Meanwhile, the graphene sheet layer of two-dimensional structure, is easy to after stripping again be stacked again, therefore makes
The method is prepared and is difficult to during Graphene obtain the few product of the piece number of plies.
In view of this, it is necessory to develop a kind of new graphene preparation method, hidden for solving safety in preparation process
Suffer from and problem of environmental pollution, enable the few Graphene of high-volume, low cost, preparation of industrialization piece layer number simultaneously again.
Content of the invention
It is an object of the invention to: for the deficiencies in the prior art, and a kind of graphene preparation method providing: Ji Jianghan
Have the material with carbon element of graphite platelet structure, containing graphite intercalation or/and peel off the reactant liquor of function component, surfactant and dynamic
Power source material adds mix homogeneously in reactor, obtains reaction paste；Carry out stripping reaction afterwards and prepare Graphene slurry,
It is finally separating purification and obtain graphene product.
To achieve these goals, the present invention adopts the following technical scheme that
A kind of preparation method of Graphene, mainly comprises the steps:
Step 1, the preparation of reaction paste: by the material with carbon element containing graphite platelet structure, contain graphite intercalation or/and stripping
The reactant liquor of function ingredients, surfactant and power source material add mix homogeneously in reactor, obtain reaction paste；
Step 2, the preparation of Graphene oleo stock: disturbance is applied to the reaction paste of step 1 so that material with carbon element and power source thing
While passing through the conducting of reactant liquor ion between matter, form electron propagation ducts, carry out graphite flake layer stripping, prepare graphite
Alkene oleo stock；
Step 3, purification: the impurity in the Graphene oleo stock that removal step 2 prepares, obtain Graphene slurry；It is dried
Obtain graphene powder material afterwards.
As a kind of improvement of the preparation method of Graphene of the present invention, material with carbon element described in step 1 includes expanded graphite, artificial
At least one in graphite and native graphite, mass ratio in reaction paste for the described material with carbon element is 0.1%-95%.
As a kind of improvement of the preparation method of Graphene of the present invention, power source material described in step 1 includes and step 1 institute
State the material that there is electric potential difference between material with carbon element, comprise rich lithium material or/and the metallicses as electrode material；Described richness lithium
Material includes lim1o2、limn2-xm2xo4、linixm31-xo2、li3-xm4xn、lifepo4、li2feo4、li7-xmnxn4、li3- xfexn2、li2s、li2s2And linixmnycozo2In at least one, wherein, m1 be co, ni, mn, cu, cr and fe at least
One kind, m2 is at least one in ni, co, cu, cr, fe and v, and m3 is in co, mn, cu, cr, fe, v, la, al, mg, ga and zn
At least one, m4 be co, ni, cu, cr and v at least one, x+y+z=1；The described metallicses as electrode material
Including at least one in lithium metal, metallic sodium, metallic potassium, magnesium metal, metallic aluminium, metallic zinc, described power source material is anti-
The mass ratio in slurry is answered to be 1%-90%.
As a kind of improvement of the preparation method of Graphene of the present invention, described in step 1, reactant liquor also includes solute and solvent,
Comprise graphite intercalation in solute or/and solvent or/and peel off function ingredients；Described solute is included with gold described in claim 3
The ion belonging to is the salt of cation, such as lithium salts, sodium salt, zinc salt etc.；Described solvent includes vinyl carbonate, propylene carbonate, fourth
Olefinic carbon acid esters, 1,2- dimethylvinylsiloxy carbonic ester, ethyl butyl carbonate, carbonic acid first butyl ester, dibutyl carbonate, diethyl carbonate, carbon
Dimethyl phthalate, trifluoromethyl ethylene carbonate, carbonic acid di-n-propyl ester, diisopropyl carbonate, Ethyl methyl carbonate, ethyl propyl carbonic acid ester,
Ethylene isopropyl ester, methyl propyl carbonate, dimethoxy-ethane, diethoxyethane, oxolane, 2- methyltetrahydrofuran, contracting
Diethylene glycol dimethyl ether, contracting TRIGLYME, contracting tetraethyleneglycol dimethyl ether, 1,3- dioxolane, dimethyl sulfoxide, ring fourth
Sulfone, 4- methyl isophthalic acid, 3- butyrolactone, gamma-butyrolacton, methyl formate, Ethyl formate, methyl acetate, ethyl acetate, methyl propionate,
At least one in ethyl propionate, methyl butyrate, ethyl n-butyrate., sub- vinyl carbonate, propane sultone and ethylene sulfite；
Described graphite intercalation or/and stripping function ingredients include alkali metal (as lithium, sodium etc.), alkali earth metal (as magnesium, calcium
Deng), metal chloride is (as zrcl4, crcl3, cocl3Deng), chloride is (as mof6, wf6Deng), rare earth element (such as sm, eu, tm,
Yb etc.), halogens (such as f, cl etc.), counterfeit halogen is (as br2, icl, if5Deng), strong acid is (as h2so4、hno3Deng), propylene carbonate
At least one in ester, its mass ratio in reaction paste is 1%-90%.
As a kind of improvement of the preparation method of Graphene of the present invention, surfactant described in step 1 comprises wetting agent, divides
Powder, penetrating agent, solubilizing agent, cosolvent, at least one in cosolvent.
As a kind of improvement of the preparation method of Graphene of the present invention, described wetting agent is anionic or/and nonionic
Type wetting agent；Described dispersant be fatty acid/aliphatic amide type/esters, paraffin class, metal soap, low molecule wax class,
At least one class in hpma；Described penetrating agent is nonionic or/and anionic penetrating agent.
As a kind of improvement of the preparation method of Graphene of the present invention, described anionic wetting agents include alkylsurfuric acid
Salt, sulfonate, fatty acid or fatty acid ester sulfate, carboxylic acid soaps, at least one in phosphate ester；Described nonionic moistening
Agent includes Polyvinylpyrrolidone, polyoxyethylated alkyl phenol, polyoxyethylene aliphatic alcohol ether, polyoxyethylene polyoxypropylene block altogether
At least one in polymers；Described dispersant is vinyl bis-stearamides, Oleic acid acyl, glycerol monostearate, three stearic acid
In glyceride, liquid paraffin, microcrystalline wax, barium stearate, zinc stearate, calcium stearate, Tissuemat E, Polyethylene Glycol at least
A kind of；Described nonionic penetrant comprises at least one in jfc, jfc-1, jfc-2, jfc-e；Described anionic infiltration
Agent comprises quickly penetrating agent t, alkali-resistant penetrant oep-70, at least one in alkali-resistant penetrant aep, seeping at high temperature agent jfc-m；
Described cosolvent include benzoic acid, sodium benzoate, salicylic acid, sodium salicylate, para-amino benzoic acid, urethane, carbamide, amide,
At least one in acetamide, Borax and potassium iodide；Described cosolvent is included in ethanol, glycerol, propylene glycol and Polyethylene Glycol
At least one.
As a kind of improvement of the preparation method of Graphene of the present invention, described in step 1, the addition of surfactant is anti-
Answer the 0.01%-30% of slurry gross mass.
A kind of disturbance improving, described in step 2, reaction paste being applied as the preparation method of Graphene of the present invention
Including stirring, ultrasonic and extruding at least one；Described in step 3, purification mode is included in centrifugation, standing sedimentation and filtration
At least one.
The Graphene that a kind of use the inventive method prepares, and the energy storage device using the preparation of this Graphene, heat
Lead device, conductance device.
The beneficial effects of the present invention is: different from traditional graphene preparation method, Graphene is prepared using this method
When:
First, the potential safety hazard in production process and problem of environmental pollution are greatly reduced: used in the present invention anti-
Answer thing non-corrosiveness, stripping reaction more gentle and do not need special high-temperature heating, safety when therefore producing in enormous quantities
High；Meanwhile, the product impurity content preparing is low it is only necessary to simple cleaning obtains pure Graphene, is therefore produced
Wastewater flow rate few, environmental pollution is little.
Secondly, greatly simplify production technology: the present invention prepares during Graphene it is only necessary to by reflection mix and blend
Graphene is prepared in achievable graphite stripping, and eliminates electrode material and prepare battery core, carry out the complicated processes of discharge and recharge afterwards again,
Process is simple, greatly reduces manufacturing cost；Meanwhile, in theory, the amount of slurry hybrid mode production Graphene is only reacted
Device size controls, and therefore easily realizes industrial mass production.
3rd it is easier to prepare the few Graphene of graphite flake layer quantity: due to there being the presence of surfactant, peels away it
Graphite flake layer afterwards will be surrounded by surfactant rapidly, prevent the Graphene generating to be stacked with, thus reduce preparing stone
The difficulty of black alkene is it is easier to prepare the few Graphene of piece layer number.
Finally, graphite flake layer stripping is only prepared Graphene, need not be destroyed graphite flake by the Graphene of present invention preparation
Rotating fields, the Graphene defect therefore preparing few (or zero defect), quality are high.
Specific embodiment
With reference to specific embodiment, the present invention and its advantage are described in detail, but the embodiment party of the present invention
Formula not limited to this.
Comparative example 1, the preparation of pre-reaction slurry: according to graphite: potassium permanganate: concentrated sulphuric acid (mass concentration is 98%): nitre
The relationship between quality of sour sodium=2.5:4.5:50:1, in 6 DEG C of reactor, adds concentrated sulphuric acid (concentration is 98%), sodium nitrate, graphite
And potassium permanganate, obtain pre-reaction slurry after stirring；
Low-temp reaction: react 4h in the environment of pre-reaction slurry obtained above is placed in 6 DEG C, that is, obtain low-temp reaction and produce
Thing；
Diluent prepare: according to deionized water: the relationship between quality of low-temp reaction product=0.5:1, select 25 DEG C go from
Sub- water, as diluent, is slowly added to dilute in above-mentioned low-temp reaction product, observes and record feed time, temperature of charge becomes
Change and the phenomenon of dilution.
Pyroreaction: diluent obtained above is warming up to 90 DEG C, keeping temperature carries out the pyroreaction of 2h afterwards, that is,
Obtain being grafted the graphite oxide slurry of oxygenated functional group；
Purification: deionized water carries out to the product after above-mentioned oxidation reaction washing → filter → wash → filter →... ...
Operation, heteroion therein is removed, obtains pure graphite oxide, is dried afterwards, smashing obtains graphite oxide powder.
Cleavage: by above-mentioned graphite oxide powder under nitrogen atmosphere, be warming up to 500 DEG C, cleavage obtains graphene powder.
Embodiment 1,
The preparation of reaction paste: select native graphite to provide source for graphite flake layer, its quality accounts for reaction paste quality
95%；
Allyl carbonate: the mixed liquor of dimethyl carbonate=1:1 is solute as the lithium hexafluoro phosphate of solvent, 1mol/l
Solution accounts for the 3% of reaction paste quality as electrolyte (reactant liquor), its quality；
Selection Polyvinylpyrrolidone is surfactant, and its quality accounts for the 1% of reaction paste quality；
Metallic lithium powder is power source material, and its quality accounts for the 1% of reaction paste quality；
Add in reactor afterwards, be thoroughly mixed and uniformly obtain reaction paste.
The preparation of Graphene oleo stock: control temperature of reactor be 150 DEG C, be sufficiently stirred for 1h so that natural graphite particles with
It is fully contacted (formation electron channel) between metallic lithium powder, have electrolyte to connect (formation ion channel) simultaneously again, carry out
Graphite flake layer stripping reaction, and in stripping process, Polyvinylpyrrolidone peels off the graphenic surface of production by being scattered in, and prevents
The generation of Graphene stacking process, thus prepare Graphene oleo stock.
Purification: be washing liquid using dimethyl carbonate, Graphene oleo stock is washed, filter, go the removal of impurity, obtain graphite
Alkene slurry；Graphene powder material is obtained after drying.
Embodiment 2,
As different from Example 1, the present embodiment comprises the steps:
The preparation of reaction paste: select native graphite to provide source for graphite flake layer, its quality accounts for reaction paste quality
50%；
Allyl carbonate: the mixed liquor of diethyl carbonate=1:1 is solute as the lithium hexafluoro phosphate of solvent, 1.2mol/l
Solution as electrolyte (reactant liquor), its quality accounts for the 10% of reaction paste quality；
Selection phosphate ester is surfactant, and its quality accounts for the 30% of reaction paste quality；
Metallic lithium powder is power source material, and its quality accounts for the 10% of reaction paste quality；
Add in reactor afterwards, be thoroughly mixed and uniformly obtain reaction paste.
The preparation of Graphene oleo stock: control temperature of reactor to be 60 DEG C, be sufficiently stirred for 30min so that natural graphite particles
It is fully contacted (formation electron channel) and metallic lithium powder between, have electrolyte to connect (formation ion channel) simultaneously again, enter
Row graphite flake layer stripping reaction, and in stripping process, phosphate ester peels off the graphenic surface of production by being scattered in, and prevents Graphene
The generation of stacking process, thus prepare Graphene oleo stock.
Purification: be washing liquid using dimethyl carbonate, Graphene oleo stock is washed, filter, go the removal of impurity, obtain graphite
Alkene slurry；Graphene powder material is obtained after drying.
Embodiment 3,
As different from Example 1, the present embodiment comprises the steps:
The preparation of reaction paste: select native graphite to provide source for graphite flake layer, its quality accounts for reaction paste quality
20%；
Allyl carbonate: the mixed liquor of diethyl carbonate=1:1 is solute as the lithium hexafluoro phosphate of solvent, 1.2mol/l
Solution as electrolyte (reactant liquor), its quality accounts for the 15% of reaction paste quality；
Selection liquid paraffin is surfactant, and its quality accounts for the 10% of reaction paste quality
Metallic lithium powder is power source material, and its quality accounts for the 55% of reaction paste quality；
Add in reactor afterwards, be thoroughly mixed and uniformly obtain reaction paste.
The preparation of Graphene oleo stock: control temperature of reactor to be 60 DEG C, be sufficiently stirred for 30min so that natural graphite particles
It is fully contacted (formation electron channel) and metallic lithium powder between, have electrolyte to connect (formation ion channel) simultaneously again, enter
Row graphite flake layer stripping reaction, and in stripping process, liquid paraffin peels off the graphenic surface of production by being scattered in, and prevents graphite
The generation of alkene stacking process, thus prepare Graphene oleo stock.
Purification: be washing liquid using dimethyl carbonate, Graphene oleo stock is washed, filter, go the removal of impurity, obtain graphite
Alkene slurry；Graphene powder material is obtained after drying.
Embodiment 4,
As different from Example 1, the present embodiment comprises the steps:
The preparation of reaction paste: select Delanium to provide source for graphite flake layer, its quality accounts for reaction paste quality
0.1%；
Allyl carbonate: the mixed liquor of diethyl carbonate=1:1 is solute as the lithium perchlorate of solvent, 1.2mol/l
Solution accounts for the 20% of reaction paste quality as electrolyte (reactant liquor), its quality；
Selection jfc is surfactant, and its quality accounts for the 0.01% of reaction paste quality；
LiFePO4 is power source material, and its quality accounts for the 79.89% of reaction paste quality；
Add in reactor afterwards, be thoroughly mixed and uniformly obtain reaction paste.
The preparation of Graphene oleo stock: control temperature of reactor be 60 DEG C, be sufficiently stirred for 1min so that synthetic graphite particles with
It is fully contacted (formation electron channel) between lithium iron phosphate particles, have electrolyte to connect (formation ion channel) simultaneously again,
Carry out graphite flake layer stripping reaction, and in stripping process, jfc peels off the graphenic surface of production by being scattered in, and prevents Graphene
The generation of stacking process, thus prepare Graphene oleo stock.
Purification: be washing liquid using dimethyl carbonate, Graphene oleo stock is washed, filter, go the removal of impurity, obtain graphite
Alkene slurry；Graphene powder material is obtained after drying.
Embodiment 5,
As different from Example 1, the present embodiment comprises the steps:
The preparation of reaction paste: select Delanium to provide source for graphite flake layer, its quality accounts for reaction paste quality
8.5%；
Allyl carbonate: the mixed liquor of diethyl carbonate=1:1 is solute as the lithium perchlorate of solvent, 1.2mol/l
Solution accounts for the 1% of reaction paste quality as electrolyte (reactant liquor), its quality；
Selection quickly penetrating agent t is surfactant, and its quality accounts for the 0.5% of reaction paste quality
Cobalt acid lithium is power source material, and its quality accounts for the 90% of reaction paste quality；
Add in reactor afterwards, be thoroughly mixed and uniformly obtain reaction paste.
The preparation of Graphene oleo stock: control temperature of reactor to be 0 DEG C, be sufficiently stirred for 48h so that synthetic graphite particles and cobalt
It is fully contacted (formation electron channel) between sour lithium granule, have electrolyte to connect (formation ion channel) simultaneously again, carry out
Graphite flake layer stripping reaction, and in stripping process, quickly penetrating agent t peels off the graphenic surface of production by being scattered in, and prevents stone
The generation of black alkene stacking process, thus prepare Graphene oleo stock.
Purification: be washing liquid using dimethyl carbonate, Graphene oleo stock is washed that centrifugation is gone the removal of impurity, obtained graphite
Alkene slurry；Graphene powder material is obtained after drying.
Embodiment 6,
As different from Example 1, the present embodiment comprises the steps:
The preparation of reaction paste: select expanded graphite to provide source for graphite flake layer, its quality accounts for reaction paste quality
5.9%；
Allyl carbonate: the mixed liquor of methyl ethyl ester=1:1 as the LiBF4 of solvent, 0.8mol/l is
The solution of solute accounts for the 90% of reaction paste quality as electrolyte (reactant liquor), its quality；
Selection fatty acid is surfactant, and its quality accounts for the 0.1% of reaction paste quality；
Metallic lithium powder is power source material, and its quality accounts for the 4% of reaction paste quality；
Add in reactor afterwards, be thoroughly mixed and uniformly obtain reaction paste.
The preparation of Graphene oleo stock: control temperature of reactor be 20 DEG C, be sufficiently stirred for 4h so that expanded graphite particles with gold
Belong to and be fully contacted (formation electron channel) between lithium powder, have electrolyte to connect (formation ion channel) simultaneously again, carry out stone
Ink sheet layer stripping reaction, and in stripping process, fatty acid peels off the graphenic surface of production by being scattered in, and prevents Graphene from stacking
The generation of process, thus prepare Graphene oleo stock.
Purification: be washing liquid using dimethyl carbonate, Graphene oleo stock is washed, filter, go the removal of impurity, obtain graphite
Alkene slurry；Graphene powder material is obtained after drying.
Embodiment 7,
As different from Example 1, the present embodiment comprises the steps:
The preparation of reaction paste: select expanded graphite to provide source for graphite flake layer, its quality accounts for reaction paste quality
18%；
Chlorosulfonic acid: the mixed liquor of sulphuric acid=1:1 is the solution of solute as electrolyte (reaction as solvent, potassium permanganate
Liquid), its quality accounts for the 18% of reaction paste quality；
Selection Polyvinylpyrrolidone is surfactant, and its quality accounts for the 5% of reaction paste quality；
LiFePO4 is power source material, and its quality accounts for the 59% of reaction paste quality；
Add in reactor afterwards, be thoroughly mixed and uniformly obtain reaction paste.
The preparation of Graphene oleo stock: control temperature of reactor be 30 DEG C, be sufficiently stirred for 10h so that expanded graphite particles with
It is fully contacted (formation electron channel) between LiFePO4, have electrolyte to connect (formation ion channel) simultaneously again, carry out
Graphite flake layer stripping reaction, and in stripping process, Polyvinylpyrrolidone peels off the graphenic surface of production by being scattered in, and prevents
The generation of Graphene stacking process, thus prepare Graphene oleo stock.Prepare Graphene oleo stock.
Purification: be washing liquid using deionized water, Graphene oleo stock is washed that centrifugation is gone the removal of impurity, obtained Graphene
Slurry；Graphene powder material is obtained after drying.
Test the impurity content of product using xps；The specific surface area of Graphene tested by specific-surface area detection instrument device.
The comparative example that a kind of contrast table can obtain with each embodiment, when preparing Graphene using the method for the present invention, prepares
Graphene impurity content low, and by optimize reactant ratio, the graphite that specific surface area is far longer than comparative example can be obtained
Alkene (prepares the Graphene that extent of exfoliation is higher, the lamella number of plies is lower).
Additionally, when the present invention prepares Graphene, purge process is simple, and the waste liquid amount of generation is few, and environmental pollution is little.
The announcement of book and teaching according to the above description, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula is changed and is changed.Therefore, the invention is not limited in above-mentioned specific embodiment, every those skilled in the art exist
On the basis of the present invention, done any conspicuously improved, replacement or modification belong to protection scope of the present invention.This
Outward, although employing some specific terms in this specification, these terms merely for convenience of description, not to the present invention
Constitute any restriction.
Claims (9)
1. a kind of preparation method of Graphene is it is characterised in that mainly comprise the steps:
Step 1, the preparation of reaction paste: by the material with carbon element containing graphite platelet structure, containing graphite intercalation or/and stripping function
The reactant liquor of component, surfactant and power source material add mix homogeneously in reactor, obtain reaction paste；
Step 2, the preparation of Graphene oleo stock: disturbance is applied to the reaction paste of step 1 so that material with carbon element and power source material it
Between by reactant liquor ion conducting while, formed electron propagation ducts, carry out graphite flake layer stripping, prepare Graphene former
Slurry；
Step 3, purification: the impurity in the Graphene oleo stock that removal step 2 prepares, obtain Graphene slurry；After drying i.e.
Obtain graphene powder material.
2. a kind of preparation method of the Graphene described in claim 1 is it is characterised in that material with carbon element described in step 1 includes expanding
At least one in graphite, Delanium and native graphite, mass ratio in reaction paste for the described material with carbon element is 0.1%-
95%.
3. a kind of preparation method of the Graphene described in claim 1 is it is characterised in that power source material described in step 1 includes
And there is the material of electric potential difference described in step 1 between material with carbon element, comprise rich lithium material or/and the metal object as electrode material
Matter；Described richness lithium material includes lim1o2、limn2-xm2xo4、linixm31-xo2、li3-xm4xn、lifepo4、li2feo4、li7- xmnxn4、li3-xfexn2、li2s、li2s2And linixmnycozo2In at least one, wherein, m1 be co, ni, mn, cu, cr and
At least one in fe, m2 be ni, co, cu, cr, fe and v at least one, m3 be co, mn, cu, cr, fe, v, la, al,
At least one in mg, ga and zn, m4 is at least one in co, ni, cu, cr and v, x+y+z=1；Described as electrode material
The metallicses of material include lithium metal, metallic sodium, metallic potassium, magnesium metal, metallic aluminium, at least one in metallic zinc；Described dynamic
Mass ratio in reaction paste for the power source material is 1%-90%.
4. a kind of preparation method of the Graphene described in claim 1 is it is characterised in that reactant liquor described in step 1 includes solute
And solvent, comprise graphite intercalation in solute or/and solvent or/and peel off function component；Described solute is included with claim 3 institute
The ion stating metal is the salt of cation；Described graphite intercalation or/and stripping function component include alkali metal, alkaline-earth metal
At least one in element, metal chloride, chloride, rare earth element, halogens, counterfeit halogen, strong acid, Allyl carbonate.
5. a kind of preparation method of the Graphene described in claim 1 is it is characterised in that surfactant described in step 1 comprises
Wetting agent, dispersant, penetrating agent, solubilizing agent, cosolvent, at least one in cosolvent.
6. the Graphene described in a kind of claim 1 preparation method it is characterised in that described wetting agent be anionic or/
And non-ionic wetting agent；Described dispersant be fatty acid/aliphatic amide type/esters, paraffin class, metal soap, low point
At least one class in sub- wax class, hpma；Described penetrating agent is nonionic or/and anionic penetrating agent.
7. a kind of preparation method of the Graphene described in claim 6 is it is characterised in that described anionic wetting agents include alkane
Base sulfate, sulfonate, fatty acid or fatty acid ester sulfate, carboxylic acid soaps, at least one in phosphate ester；Described nonionic
Type wetting agent include polyoxyethylated alkyl phenol, polyoxyethylene aliphatic alcohol ether, in polyoxyethylene polyoxypropylene block copolymer
At least one；Described dispersant is vinyl bis-stearamides, Oleic acid acyl, glycerol monostearate, glyceryl tristearate, liquid
At least one in body paraffin, microcrystalline wax, barium stearate, zinc stearate, calcium stearate, Tissuemat E, Polyethylene Glycol；Described
Nonionic penetrant comprises at least one in jfc, jfc-1, jfc-2, jfc-e；Described anionic penetrating agent comprises soon
At least one in fast penetrating agent t, alkali-resistant penetrant oep-70, alkali-resistant penetrant aep, seeping at high temperature agent jfc-m；Described hydrotropy
Agent includes benzoic acid, sodium benzoate, salicylic acid, sodium salicylate, para-amino benzoic acid, urethane, carbamide, amide, acetamide, boron
At least one in sand and potassium iodide；Described cosolvent includes at least one in ethanol, glycerol, propylene glycol and Polyethylene Glycol.
8. a kind of preparation method of the Graphene described in claim 1 is it is characterised in that adding of surfactant described in step 1
Dosage is the 0.01%-30% of reactant gross mass.
9. a kind of preparation method of the Graphene described in claim 1 is it is characterised in that applied to reaction paste described in step 2
Plus disturbance include stir, ultrasonic, extruding at least one；Way of purification described in step 3 includes centrifugation, standing sedimentation, mistake
At least one in filter.
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| CN201510274571.9A CN104860311B (en) | 2015-05-26 | 2015-05-26 | Preparation method of graphene |
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| CN105621404B (en) * | 2016-02-19 | 2017-12-22 | 成都新柯力化工科技有限公司 | It is a kind of that the method for preparing graphene microchip is peeled off by sticky mechanical shearing |
| US11247906B2 (en) * | 2016-03-09 | 2022-02-15 | Global Graphene Group, Inc. | Electrochemical production of graphene sheets directly from graphite mineral |
| CN105819437B (en) * | 2016-05-06 | 2018-01-30 | 成都新柯力化工科技有限公司 | A kind of method that scale cleaning prepares graphene |
| CN106006613A (en) * | 2016-05-24 | 2016-10-12 | 广州市霆宇能源科技有限责任公司 | Method for preparing graphene |
| CN105836741A (en) * | 2016-05-31 | 2016-08-10 | 成都新柯力化工科技有限公司 | Method for preparing graphene nanoplatelets by miniature blasting |
| US10435797B2 (en) | 2016-06-26 | 2019-10-08 | Global Graphene Group, Inc. | Electrochemical production of graphene sheets from coke or coal |
| CN106566302B (en) * | 2016-10-20 | 2018-05-11 | 深圳市蓝水海洋高端装备研究院有限公司 | A kind of graphene composite dispersion liquid for anticorrosive paint and preparation method thereof |
| CN109467658A (en) * | 2018-11-13 | 2019-03-15 | 大同新成新材料股份有限公司 | A kind of preparation method and preparation facilities of modified graphene slurry |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011162727A1 (en) * | 2010-06-25 | 2011-12-29 | National University Of Singapore | Methods of forming graphene by graphite exfoliation |
| CN102315423A (en) * | 2010-07-08 | 2012-01-11 | 中国科学院宁波材料技术与工程研究所 | Graphene/lithium iron phosphate compound anode material, preparation method thereof and lithium ion secondary battery |
| CN102372268A (en) * | 2011-10-18 | 2012-03-14 | 浙江大学 | Preparation method of graphene material |
| CN103183331A (en) * | 2011-12-28 | 2013-07-03 | 清华大学 | Preparation method for graphene |
-
2015
- 2015-05-26 CN CN201510274571.9A patent/CN104860311B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011162727A1 (en) * | 2010-06-25 | 2011-12-29 | National University Of Singapore | Methods of forming graphene by graphite exfoliation |
| CN102315423A (en) * | 2010-07-08 | 2012-01-11 | 中国科学院宁波材料技术与工程研究所 | Graphene/lithium iron phosphate compound anode material, preparation method thereof and lithium ion secondary battery |
| CN102372268A (en) * | 2011-10-18 | 2012-03-14 | 浙江大学 | Preparation method of graphene material |
| CN103183331A (en) * | 2011-12-28 | 2013-07-03 | 清华大学 | Preparation method for graphene |
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