CN104860311A - Preparation method of graphene - Google Patents
Preparation method of graphene Download PDFInfo
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- CN104860311A CN104860311A CN201510274571.9A CN201510274571A CN104860311A CN 104860311 A CN104860311 A CN 104860311A CN 201510274571 A CN201510274571 A CN 201510274571A CN 104860311 A CN104860311 A CN 104860311A
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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 a kind of preparation method of Graphene.
Background technology
2004, strong K sea nurse (Andre K.Geim) of peace moral etc. of Univ Manchester UK adopted mechanically peel method to prepare Graphene (Graphene) first, has pulled open the prelude of the preparation of this material, operational research thus.So-called Graphene, refers to a kind of plates of the arrangement in hexagonal annular between carbon atom, is usually made up of single or multiple lift graphite flake layer, infinitely can extends at two-dimensional space, can be described as proper two-dirnentional structure material.It has the outstanding advantages such as specific surface area is large, electrical and thermal conductivity performance is excellent, thermal expansivity is low: specifically, high specific surface area (calculated value: 2630m
2/ g); High conductivity, carrier transport rate (200000cm
2/ Vs); High heat conductance (5000W/mK); High strength, high Young's modulus (1100GPa), breaking tenacity (125GPa).Therefore its in energy storage field, thermal conduction field and Materials with High Strength field have great utilization prospect.
The existing method preparing Graphene mainly contains micromechanics stripping method, ultrahigh vacuum(HHV) Graphene epitaxial growth method, oxidation-reduction method, chemical Vapor deposition process (CVD), solvent stripping method, electrolytic process and solvent-thermal method.In this serial of methods, oxidation-reduction method and electrolytic process realize the preferred version that Graphene prepared in enormous quantities.
But when adopting oxidation style to prepare graphite oxide, the oxygenant used is the oxygenant such as the vitriol oil, potassium permanganate often; And in order to more fully by graphite oxidation, often need to carry out pyroreaction.Therefore there is great potential safety hazard in preparation process, and oxygenant Problem of Failure can occur, cause the failure of whole oxidizing reaction; Meanwhile, in preparation process, a large amount of waste liquids can be produced, cause the increase of environmental pollution and manufacturing cost.
Comparatively speaking, when electrochemical method prepares Graphene, the reactant used normally electrolytic solution, its potential safety hazard is in operation low, and environmental pollution is little.As the method (application number CN201110269176.3) of a kind of preparing graphene by electrochemical stripping of people's inventions such as Sun Feng, first use the pole piece of graphitiferous material, containing lithium to electrode plates, be assembled into battery containing the electrolytic solution of propylene carbonate (PC) and barrier film, make solvation Lithium-ion embeding graphite layers by discharging or charging, final graphite peels off formation Graphene layer by layer.Relative to prior art, when the present invention fully takes into account non-compatibility and the discharge and recharge of graphite and PC, lithium ion can insert the feature in graphite layer by layer, makes graphite be completely solvated lithium ion layer by layer and inserts and be finally stripped generation Graphene.The method of this preparing graphene by electrochemical stripping is without the need to using the equipment of complex and expensive, simple to operate, and only needs to carry out simple discharge and recharge and aftertreatment just can obtain Graphene.But become by electrode assembling in the process of battery core, manufacturing cost is high, and due to the control of electrode applied thickness, the Graphene product amount obtained is few, is difficult to realize industrial mass preparation; Meanwhile, the graphene sheet layer of two-dirnentional structure, is easy to after stripping again be stacked again, is difficult to obtain the sheet number of plies few product when therefore making the method prepare Graphene.
In view of this, a kind of new graphene preparation method of necessary exploitation, for solving potential safety hazard and problem of environmental pollution in preparation process, can realize again in enormous quantities, low cost, Graphene that preparation of industrialization lamella quantity is few simultaneously.
Summary of the invention
The object of the invention is to: for the deficiencies in the prior art, and a kind of graphene preparation method provided: be about to the carbon material containing graphite platelet structure, containing graphite intercalation or/and peel off the reaction solution of function component, tensio-active agent and propulsion source material and add in reactor and mix, obtain reaction paste; Carry out stripping reaction afterwards and prepare Graphene slurry, namely last separation and purification obtains graphene product.
To achieve these goals, the present invention adopts following technical scheme:
A preparation method for Graphene, mainly comprises the steps:
Step 1, the preparation of reaction paste: by the carbon material containing graphite platelet structure, containing graphite intercalation or/and peel off the reaction solution of function ingredients, tensio-active agent and propulsion source material and add in reactor and mix, obtain reaction paste;
Step 2, the preparation of Graphene magma: disturbance is applied to the reaction paste of step 1, makes by while the conducting of reaction solution ion between carbon material and propulsion source material, form electron propagation ducts, carry out graphite flake layer stripping, prepare Graphene magma;
Step 3, purifies: the impurity in the Graphene magma that removal step 2 prepares, obtains Graphene slurry; Namely graphene powder material is obtained after drying.
One as the preparation method of Graphene of the present invention is improved, and carbon material described in step 1 comprises at least one in expanded graphite, synthetic graphite and natural graphite, and the mass ratio of described carbon material in reaction paste is 0.1%-95%.
One as the preparation method of Graphene of the present invention is improved, and propulsion source material described in step 1 comprises and there is the material of potential difference described in step 1 between carbon material, comprises rich lithium material or/and as the metallics of electrode materials; Described rich lithium material comprises LiM1O
2, LiMn
2-Xm2
xo
4, LiNi
xm3
1-xo
2, Li
3-xm4
xn, LiFePO
4, Li
2feO
4, Li
7-xmn
xn
4, Li
3-xfe
xn
2, Li
2s, Li
2s
2and LiNi
xmn
yco
zo
2in at least one, wherein, M1 is at least one in Co, Ni, Mn, Cu, Cr and Fe, M2 is at least one in Ni, Co, Cu, Cr, Fe and V, M3 is at least one in Co, Mn, Cu, Cr, Fe, V, La, Al, Mg, Ga and Zn, M4 is at least one in Co, Ni, Cu, Cr and V, x+y+z=1; The described metallics as electrode materials comprises at least one in metallic lithium, sodium Metal 99.5, potassium metal, MAGNESIUM METAL, metallic aluminium, metallic zinc, and the mass ratio of described propulsion source material in reaction paste is 1%-90%.
One as the preparation method of Graphene of the present invention is improved, and reaction solution described in step 1 also comprises solute and solvent, and solute is or/and comprise graphite intercalation in solvent or/and peel off function ingredients, it is cationic salt that described solute comprises with the ion of metal described in claim 3, as lithium salts, sodium salt, zinc salt etc., described solvent comprises vinyl carbonate, propylene carbonate, butylene carbonic ether, 1, 2-dimethylvinylsiloxy carbonic ether, ethyl butyl carbonate, carbonic acid first butyl ester, dibutyl carbonate, diethyl carbonate, methylcarbonate, trifluoromethyl NSC 11801, carbonic acid di-n-propyl ester, diisopropyl carbonate, Methyl ethyl carbonate, ethyl propyl carbonic acid ester, ethylene isopropyl ester, methyl propyl carbonate, glycol dimethyl ether, diethoxyethane, tetrahydrofuran (THF), 2-methyltetrahydrofuran, diglycol ethylene dme, contracting TRIGLYME, contracting tetraethyleneglycol dimethyl ether, 1, 3-dioxolane, dimethyl sulfoxide (DMSO), tetramethylene sulfone, 4-methyl isophthalic acid, 3-butyrolactone, gamma-butyrolactone, methyl-formiate, ethyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl-butyrate, ethyl butyrate, sub-vinyl carbonate, at least one in propane sultone and ethene sulfite, described graphite intercalation comprises alkali metal (as lithium, sodium etc.), alkali earth metal (as magnesium, calcium etc.), metal chloride (as ZrCl or/and peel off function ingredients
4, CrCl
3, CoCl
3deng), muriate is (as MoF
6, WF
6deng), rare earth element (as Sm, Eu, Tm, Yb etc.), halogens (as F, Cl etc.), counterfeit halogen be (as Br
2, ICl, IF
5deng), strong acid is (as H
2sO
4, HNO
3deng), at least one in propylene carbonate, its mass ratio in reaction paste is 1%-90%.
One as the preparation method of Graphene of the present invention is improved, and tensio-active agent described in step 1 comprises at least one in wetting agent, dispersion agent, permeate agent, solubilizing agent, solubility promoter, latent solvent.
One as the preparation method of Graphene of the present invention is improved, and described wetting agent is that anionic is or/and non-ionic wetting agent; Described dispersion agent is at least one class in fatty acid/aliphatic amide type/ester class, paraffin class, metal soap, low-molecular-weight wax class, HPMA; Described permeate agent is that non-ionic type is or/and anionic permeate agent.
One as the preparation method of Graphene of the present invention is improved, and described anionic wetting agents comprises at least one in alkyl-sulphate, sulfonate, lipid acid or fatty acid ester vitriol, carboxylic soap class, phosphoric acid ester; Described non-ionic wetting agent comprises at least one in polyvinylpyrrolidone, polyxyethylated alkylphenol, polyoxyethylene aliphatic alcohol ether, polyoxyethylene polyoxypropylene block copolymer; Described dispersion agent is at least one in vinyl bis-stearamides, oleic acid acyl, glyceryl monostearate, Tristearoylglycerol, whiteruss, microcrystalline wax, barium stearate, Zinic stearas, calcium stearate, polyethylene wax, polyoxyethylene glycol; Described nonionic penetrant comprises at least one in JFC, JFC-1, JFC-2, JFC-E; Described anionic permeate agent comprises at least one in fast penetrant T, alkali-resistant penetrant OEP-70, alkali-resistant penetrant AEP, seeping at high temperature agent JFC-M; Described solubility promoter comprises at least one in phenylformic acid, Sodium Benzoate, Whitfield's ointment, sodium salicylate, para-amino benzoic acid, urethane, urea, acid amides, ethanamide, borax and potassiumiodide; Described latent solvent comprises at least one in ethanol, glycerine, propylene glycol and polyoxyethylene glycol.
One as the preparation method of Graphene of the present invention is improved, and the addition of tensio-active agent described in step 1 is the 0.01%-30% of reaction paste total mass.
One as the preparation method of Graphene of the present invention is improved, the disturbance described in step 2, reaction paste applied comprise stirring, ultrasonic and extruding at least one; Purification mode described in step 3 comprises at least one in centrifugal, standing sedimentation and filtration.
Use the Graphene that the inventive method prepares, and the energy storage device using this Graphene to prepare, thermal conductance device, conductance device.
Beneficial effect of the present invention is: different from traditional graphene preparation method, when adopting present method to prepare Graphene:
First, greatly reduce the potential safety hazard in production process and problem of environmental pollution: reactant non-corrosiveness used in the present invention, stripping reaction are comparatively gentle and do not need special heat, when therefore producing in enormous quantities, security is high; Meanwhile, the product impurity content prepared is low, and only need simple cleaning namely to obtain pure Graphene, therefore produced wastewater flow rate is few, and environmental pollution is little.
Secondly, greatly simplify production technique: when the present invention prepares Graphene, only need reflection mix and blend to realize graphite and peel off and prepare Graphene, and eliminate electrode materials and prepare battery core, carry out the complicated processes of discharge and recharge afterwards again, technique is simple, greatly reduces manufacturing cost; Meanwhile, in theory, the amount that slurry hybrid mode produces Graphene only controls by reactor size, therefore very easily realizes industrialized mass.
3rd, more easily prepare the Graphene that graphite flake layer quantity is few: owing to there being the existence of tensio-active agent, graphite flake layer after peeling away will be surrounded by tensio-active agent rapidly, prevent the Graphene of generation mutually stacking, thus reduce the difficulty preparing Graphene, more easily prepare the Graphene that lamella quantity is few.
Finally, Graphene prepared by the present invention, be only peeled off by graphite flake layer to prepare Graphene, without the need to destroying graphite platelet structure, the Graphene defect therefore prepared few (or zero defect), quality are high.
Embodiment
Below in conjunction with embodiment, the present invention and beneficial effect thereof are described in detail, but embodiments of the present invention are not limited thereto.
Comparative example 1, the preparation of pre-reaction slurry: according to graphite: potassium permanganate: the vitriol oil (mass concentration is 98%): the relationship between quality of SODIUMNITRATE=2.5:4.5:50:1, at the reactor of 6 DEG C, add the vitriol oil (concentration is 98%), SODIUMNITRATE, graphite and potassium permanganate, after stirring, obtain pre-reaction slurry;
Low-temp reaction: react 4h under pre-reaction slurry obtained above is placed in the environment of 6 DEG C, namely obtain low-temp reaction product;
Prepared by diluent: according to deionized water: the relationship between quality of low-temp reaction product=0.5:1, select the deionized water of 25 DEG C as thinner, in above-mentioned low-temp reaction product, slowly add dilution, observe and record feed time, temperature of charge change and the phenomenon of dilution.
Pyroreaction: diluent obtained above is warming up to 90 DEG C, keeps temperature to carry out the pyroreaction of 2h afterwards, namely obtains the graphite oxide slurry of grafting oxygenated functional group;
Purifying: with deionized water to the product after above-mentioned oxidizing reaction wash → filter → to wash → filter →... ... operation, removes hetero-ion wherein, obtains pure graphite oxide, afterwards dry, shatter and obtain 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 natural graphite to be graphite flake layer providing source, its quality accounts for 95% of reaction paste quality;
Propylene carbonate: the mixed solution of methylcarbonate=1:1 as the lithium hexafluoro phosphate of solvent, 1mol/L be the solution of solute as electrolytic solution (reaction solution), its quality accounts for 3% of reaction paste quality;
Selection polyvinylpyrrolidone is tensio-active agent, and its quality accounts for 1% of reaction paste quality;
Metallic lithium powder is propulsion source material, and its quality accounts for 1% of reaction paste quality;
Add afterwards in reactor, be fully uniformly mixed and obtain reaction paste.
The preparation of Graphene magma: controlling temperature of reactor is 150 DEG C, abundant stirring 1h, make fully to contact between natural graphite particles with metallic lithium powder (formation electron channel), there is again electrolytic solution to connect (formation ionic channel) simultaneously, carry out graphite flake layer stripping reaction, and in stripping process, polyvinylpyrrolidone will be scattered in the graphenic surface peeled off and produce, prevent the generation of the stacking process of Graphene, thus prepare Graphene magma.
Purify: employing methylcarbonate is washing lotion, washs Graphene magma, filter, remove impurity, obtain Graphene slurry; Namely 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 natural graphite to be graphite flake layer providing source, its quality accounts for 50% of reaction paste quality;
Propylene carbonate: the mixed solution of diethyl carbonate=1:1 as the lithium hexafluoro phosphate of solvent, 1.2mol/L be the solution of solute as electrolytic solution (reaction solution), its quality accounts for 10% of reaction paste quality;
Selection phosphoric acid ester is tensio-active agent, and its quality accounts for 30% of reaction paste quality;
Metallic lithium powder is propulsion source material, and its quality accounts for 10% of reaction paste quality;
Add afterwards in reactor, be fully uniformly mixed and obtain reaction paste.
The preparation of Graphene magma: controlling temperature of reactor is 60 DEG C, abundant stirring 30min, make fully to contact between natural graphite particles with metallic lithium powder (formation electron channel), there is again electrolytic solution to connect (formation ionic channel) simultaneously, carry out graphite flake layer stripping reaction, and in stripping process, phosphoric acid ester will be scattered in the graphenic surface peeled off and produce, prevent the generation of the stacking process of Graphene, thus prepare Graphene magma.
Purify: employing methylcarbonate is washing lotion, washs Graphene magma, filter, remove impurity, obtain Graphene slurry; Namely 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 natural graphite to be graphite flake layer providing source, its quality accounts for 20% of reaction paste quality;
Propylene carbonate: the mixed solution of diethyl carbonate=1:1 as the lithium hexafluoro phosphate of solvent, 1.2mol/L be the solution of solute as electrolytic solution (reaction solution), its quality accounts for 15% of reaction paste quality;
Selection whiteruss is tensio-active agent, and its quality accounts for 10% of reaction paste quality
Metallic lithium powder is propulsion source material, and its quality accounts for 55% of reaction paste quality;
Add afterwards in reactor, be fully uniformly mixed and obtain reaction paste.
The preparation of Graphene magma: controlling temperature of reactor is 60 DEG C, abundant stirring 30min, make fully to contact between natural graphite particles with metallic lithium powder (formation electron channel), there is again electrolytic solution to connect (formation ionic channel) simultaneously, carry out graphite flake layer stripping reaction, and in stripping process, whiteruss will be scattered in the graphenic surface peeled off and produce, prevent the generation of the stacking process of Graphene, thus prepare Graphene magma.
Purify: employing methylcarbonate is washing lotion, washs Graphene magma, filter, remove impurity, obtain Graphene slurry; Namely 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 synthetic graphite to be graphite flake layer providing source, its quality accounts for 0.1% of reaction paste quality;
Propylene carbonate: the mixed solution of diethyl carbonate=1:1 as the lithium perchlorate of solvent, 1.2mol/L be the solution of solute as electrolytic solution (reaction solution), its quality accounts for 20% of reaction paste quality;
Selection JFC is tensio-active agent, and its quality accounts for 0.01% of reaction paste quality;
Iron lithium phosphate is propulsion source material, and its quality accounts for 79.89% of reaction paste quality;
Add afterwards in reactor, be fully uniformly mixed and obtain reaction paste.
The preparation of Graphene magma: controlling temperature of reactor is 60 DEG C, abundant stirring 1min, make fully to contact between synthetic graphite particles with lithium iron phosphate particles (formation electron channel), there is again electrolytic solution to connect (formation ionic channel) simultaneously, carry out graphite flake layer stripping reaction, and in stripping process, JFC will be scattered in the graphenic surface peeled off and produce, prevent the generation of the stacking process of Graphene, thus prepare Graphene magma.
Purify: employing methylcarbonate is washing lotion, washs Graphene magma, filter, remove impurity, obtain Graphene slurry; Namely 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 synthetic graphite to be graphite flake layer providing source, its quality accounts for 8.5% of reaction paste quality;
Propylene carbonate: the mixed solution of diethyl carbonate=1:1 as the lithium perchlorate of solvent, 1.2mol/L be the solution of solute as electrolytic solution (reaction solution), its quality accounts for 1% of reaction paste quality;
Selection fast penetrant T is tensio-active agent, and its quality accounts for 0.5% of reaction paste quality
Cobalt acid lithium is propulsion source material, and its quality accounts for 90% of reaction paste quality;
Add afterwards in reactor, be fully uniformly mixed and obtain reaction paste.
The preparation of Graphene magma: controlling temperature of reactor is 0 DEG C, abundant stirring 48h, make fully to contact (formation electron channel) between synthetic graphite particles with cobalt acid lithium particle, there is again electrolytic solution to connect (formation ionic channel) simultaneously, carry out graphite flake layer stripping reaction, and in stripping process, fast penetrant T will be scattered in the graphenic surface peeled off and produce, prevent the generation of the stacking process of Graphene, thus prepare Graphene magma.
Purify: employing methylcarbonate is washing lotion, washs Graphene magma, centrifugal, remove impurity, obtain Graphene slurry; Namely 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 be graphite flake layer providing source, its quality accounts for 5.9% of reaction paste quality;
Propylene carbonate: the mixed solution of methyl ethyl ester=1:1 as the LiBF4 of solvent, 0.8mol/L be the solution of solute as electrolytic solution (reaction solution), its quality accounts for 90% of reaction paste quality;
Selection lipid acid is tensio-active agent, and its quality accounts for 0.1% of reaction paste quality;
Metallic lithium powder is propulsion source material, and its quality accounts for 4% of reaction paste quality;
Add afterwards in reactor, be fully uniformly mixed and obtain reaction paste.
The preparation of Graphene magma: controlling temperature of reactor is 20 DEG C, abundant stirring 4h, make fully to contact between expanded graphite particles with metallic lithium powder (formation electron channel), there is again electrolytic solution to connect (formation ionic channel) simultaneously, carry out graphite flake layer stripping reaction, and in stripping process, lipid acid will be scattered in the graphenic surface peeled off and produce, prevent the generation of the stacking process of Graphene, thus prepare Graphene magma.
Purify: employing methylcarbonate is washing lotion, washs Graphene magma, filter, remove impurity, obtain Graphene slurry; Namely 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 be graphite flake layer providing source, its quality accounts for 18% of reaction paste quality;
Chlorsulfonic acid: the mixed solution of sulfuric acid=1:1 as solvent, potassium permanganate be the solution of solute as electrolytic solution (reaction solution), its quality accounts for 18% of reaction paste quality;
Selection polyvinylpyrrolidone is tensio-active agent, and its quality accounts for 5% of reaction paste quality;
Iron lithium phosphate is propulsion source material, and its quality accounts for 59% of reaction paste quality;
Add afterwards in reactor, be fully uniformly mixed and obtain reaction paste.
The preparation of Graphene magma: controlling temperature of reactor is 30 DEG C, abundant stirring 10h, make fully to contact between expanded graphite particles with iron lithium phosphate (formation electron channel), there is again electrolytic solution to connect (formation ionic channel) simultaneously, carry out graphite flake layer stripping reaction, and in stripping process, polyvinylpyrrolidone will be scattered in the graphenic surface peeled off and produce, prevent the generation of the stacking process of Graphene, thus prepare Graphene magma.Prepare Graphene magma.
Purify: employing deionized water is washing lotion, washs Graphene magma, centrifugal, remove impurity, obtain Graphene slurry; Namely graphene powder material is obtained after drying.
XPS is adopted to test the foreign matter content of product; The specific surface area of specific-surface area detection instrument device test Graphene.
The comparative example that contrast table is a kind and each embodiment can obtain, when adopting method of the present invention to prepare Graphene, the Graphene foreign matter content prepared is low, and by optimizing reactant ratio, the Graphene (namely preparing the Graphene that extent of exfoliation is higher, the lamella number of plies is lower) that specific surface area is far longer than comparative example can be obtained.
In addition, 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 instruction according to the above description, those skilled in the art in the invention can also change above-mentioned embodiment and revise.Therefore, the present invention is not limited to above-mentioned embodiment, and any apparent improvement of every those skilled in the art done by basis of the present invention, replacement or modification all belong to protection scope of the present invention.In addition, although employ some specific terms in this specification sheets, these terms just for convenience of description, do not form any restriction to the present invention.
Claims (10)
1. a preparation method for Graphene, is characterized in that, mainly comprises the steps:
Step 1, the preparation of reaction paste: by the carbon material containing graphite platelet structure, containing graphite intercalation or/and peel off the reaction solution of function ingredients, tensio-active agent and propulsion source material and add in reactor and mix, obtain reaction paste;
Step 2, the preparation of Graphene magma: disturbance is applied to the reaction paste of step 1, makes by while the conducting of reaction solution ion between carbon material and propulsion source material, form electron propagation ducts, carry out graphite flake layer stripping, prepare Graphene magma;
Step 3, purifies: the impurity in the Graphene magma that removal step 2 prepares, obtains Graphene slurry; Namely graphene powder material is obtained after drying.
2. a preparation method for Graphene according to claim 1, is characterized in that, carbon material described in step 1 comprises at least one in expanded graphite, synthetic graphite and natural graphite, and the mass ratio of described carbon material in reaction paste is 0.1%-95%.
3. a preparation method for Graphene according to claim 1, is characterized in that, propulsion source material described in step 1 comprises and there is the material of potential difference described in step 1 between carbon material, comprises rich lithium material or/and as the metallics of electrode materials; Described rich lithium material comprises LiM1O
2, LiMn
2-Xm2
xo
4, LiNi
xm3
1-xo
2, Li
3-xm4
xn, LiFePO
4, Li
2feO
4, Li
7-xmn
xn
4, Li
3-xfe
xn
2, Li
2s, Li
2s
2and LiNi
xmn
yco
zo
2in at least one, wherein, M1 is at least one in Co, Ni, Mn, Cu, Cr and Fe, M2 is at least one in Ni, Co, Cu, Cr, Fe and V, M3 is at least one in Co, Mn, Cu, Cr, Fe, V, La, Al, Mg, Ga and Zn, M4 is at least one in Co, Ni, Cu, Cr and V, x+y+z=1; The described metallics as electrode materials comprises at least one in metallic lithium, sodium Metal 99.5, potassium metal, MAGNESIUM METAL, metallic aluminium, metallic zinc, and the mass ratio of described propulsion source material in reaction paste is 1%-90%.
4. a preparation method for Graphene according to claim 1, is characterized in that, reaction solution described in step 1 also comprises solute and solvent, and solute is or/and comprise graphite intercalation in solvent or/and peel off function ingredients; It is cationic salt that described solute comprises with the ion of metal described in claim 3; Described graphite intercalation is or/and stripping function ingredients comprises at least one in alkali metal, alkali earth metal, metal chloride, muriate, rare earth element, halogens, counterfeit halogen, strong acid, propylene carbonate, and described graphite intercalation is or/and peeling off the mass ratio of function ingredients in reaction paste is 1%-90%.
5. a preparation method for Graphene according to claim 1, is characterized in that, tensio-active agent described in step 1 comprises at least one in wetting agent, dispersion agent, permeate agent, solubilizing agent, solubility promoter, latent solvent.
6. a preparation method for Graphene according to claim 5, is characterized in that, described wetting agent is that anionic is or/and non-ionic wetting agent; Described dispersion agent is at least one class in fatty acid/aliphatic amide type/ester class, paraffin class, metal soap, low-molecular-weight wax class, HPMA; Described permeate agent is that non-ionic type is or/and anionic permeate agent.
7. a preparation method for Graphene according to claim 6, is characterized in that, described anionic wetting agents comprises at least one in alkyl-sulphate, sulfonate, lipid acid or fatty acid ester vitriol, carboxylic soap class, phosphoric acid ester; Described non-ionic wetting agent comprises at least one in polyvinylpyrrolidone, polyxyethylated alkylphenol, polyoxyethylene aliphatic alcohol ether, polyoxyethylene polyoxypropylene block copolymer; Described dispersion agent is at least one in vinyl bis-stearamides, oleic acid acyl, glyceryl monostearate, Tristearoylglycerol, whiteruss, microcrystalline wax, barium stearate, Zinic stearas, calcium stearate, polyethylene wax, polyoxyethylene glycol; Described nonionic penetrant comprises at least one in JFC, JFC-1, JFC-2, JFC-E; Described anionic permeate agent comprises at least one in fast penetrant T, alkali-resistant penetrant OEP-70, alkali-resistant penetrant AEP, seeping at high temperature agent JFC-M; Described solubility promoter comprises at least one in phenylformic acid, Sodium Benzoate, Whitfield's ointment, sodium salicylate, para-amino benzoic acid, urethane, urea, acid amides, ethanamide, borax and potassiumiodide; Described latent solvent comprises at least one in ethanol, glycerine, propylene glycol and polyoxyethylene glycol.
8. a preparation method for Graphene according to claim 1, is characterized in that, the addition of tensio-active agent described in step 1 is the 0.01%-30% of reaction paste total mass.
9. a preparation method for Graphene according to claim 1, is characterized in that, the disturbance described in step 2, reaction paste applied comprise stirring, ultrasonic and extruding at least one; Purification mode described in step 3 comprises at least one in centrifugal, standing sedimentation and filtration.
10. use the Graphene that method described in claim 1 prepares, and the energy storage device using this Graphene to prepare, thermal conductance device, conductance device.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105621404A (en) * | 2016-02-19 | 2016-06-01 | 成都新柯力化工科技有限公司 | Method for preparing graphene nanoplatelets by viscously mechanical shearing and stripping |
| CN105819437A (en) * | 2016-05-06 | 2016-08-03 | 成都新柯力化工科技有限公司 | Method for large-scale clean graphene preparation |
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| 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 |
| CN106566302A (en) * | 2016-10-20 | 2017-04-19 | 成都新柯力化工科技有限公司 | Graphene composite dispersion liquid for anticorrosion coating and preparation method thereof |
| CN108778985A (en) * | 2016-03-09 | 2018-11-09 | 纳米技术仪器公司 | Directly by graphite mineral electrochemical production graphene film |
| CN109328104A (en) * | 2016-06-26 | 2019-02-12 | 纳米技术仪器公司 | By coke or coal electrochemical production graphene film |
| 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 |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105621404A (en) * | 2016-02-19 | 2016-06-01 | 成都新柯力化工科技有限公司 | Method for preparing graphene nanoplatelets by viscously mechanical shearing and stripping |
| CN108778985A (en) * | 2016-03-09 | 2018-11-09 | 纳米技术仪器公司 | Directly by graphite mineral electrochemical production graphene film |
| CN105819437A (en) * | 2016-05-06 | 2016-08-03 | 成都新柯力化工科技有限公司 | Method for large-scale clean graphene preparation |
| 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 |
| CN109328104A (en) * | 2016-06-26 | 2019-02-12 | 纳米技术仪器公司 | By coke or coal electrochemical production graphene film |
| US11560631B2 (en) | 2016-06-26 | 2023-01-24 | Global Graphene Group, Inc. | Electrochemical production of graphene sheets from coke or coal |
| CN106566302A (en) * | 2016-10-20 | 2017-04-19 | 成都新柯力化工科技有限公司 | Graphene composite dispersion liquid for anticorrosion coating and preparation method thereof |
| 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 |
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