CN109835887A - A kind of preparation method of graphene - Google Patents
A kind of preparation method of graphene Download PDFInfo
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- CN109835887A CN109835887A CN201711188245.1A CN201711188245A CN109835887A CN 109835887 A CN109835887 A CN 109835887A CN 201711188245 A CN201711188245 A CN 201711188245A CN 109835887 A CN109835887 A CN 109835887A
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Abstract
The invention discloses a kind of preparation methods of graphene, comprising: uniform stirring in the mixed solution of sulfuric acid and nitric acid is added in 5g natural graphite powder, is slow added into 55g potassium chlorate；It after mixed liquor stirs 96 hours at room temperature, repeats that 5% hydrochloric acid solution is added and is centrifuged, until there is no any sulfate ion to exist in solution, being diluted with a large amount of deionized water and being centrifuged until the presentation of filtrate pH value is neutral；Neutral solution will be presented with the filter paper filtering in 0.5 μm of aperture, to take out after toasting rs for 24 hours at 80 DEG C, graphite oxide powder is obtained after grinding with agate mortar；The graphite oxide prepared is put into cast high temperature furnace again, it first carries out vacuumizing 5 minutes, it is passed through argon gas again 30 minutes, is that 60 DEG C/min is warming up to 1100 DEG C with heating rate to prevent external air from entering and influence process, hold temperature one hour, when being heated up, it is continually fed into argon gas 100sccm, then is passed through hydrogen 20sccm, increase reduction effect, oxidable graphite thermal is removed, graphene is made.
Description
Technical field
The present invention relates to a kind of preparation method of graphite material, especially a kind of preparation method of graphene.
Background technique
With known, as petroleum is largely exploited, unconfined use, waste gas sent off from automobiles causes severe air dirty
Dye, cause all over the world weather tempestuously change, and then cause greenhouse effects cause ozone layer broken hole, face air pollution and energy
Energy saving various solution is energetically looked in succession by the Double jeopardy of source exhaustion, various countries.
Although phase-change material has the advantages that potential heat value is big, but have heat biography number too low and the fatal defects of melted by heat deformation
Extremely to be solved, many scholars at home and abroad attempt hot transfer efficiency and curable type ability that phase-change material is improved using various filling material,
The scholars such as Mills and Sari add porous graphite and expanded graphite in phase-change material, but need to dose carbon materials to 10wt.%. with
On begin to improve the hot biography ability of phase-change material, but the carbon materials for adding volume cause the potential heat value and resistance of phase-change material instead
Rate decline, has foreign scholar also in addition in order to solve the problems, such as phase-change material melted by heat and deformation, adds in phase-change material
The macromolecules such as high density polyethylene (HDPE) as backing material, but allow the hot transfer efficiency of phase-change material more
Deteriorate.
Summary of the invention
To solve existing technical problem, the purpose of the present invention is to provide a kind of preparation methods of graphene.
For above-mentioned purpose, the preparation method of graphene provided by the invention, comprising: sulphur is added in 5g natural graphite powder
Acid and uniform stirring in the mixed solution of nitric acid, are slow added into 55g potassium chlorate；After mixed liquor stirs 96 hours at room temperature,
It repeats that 5% hydrochloric acid solution is added and is centrifuged, until there is no any sulfate ion to exist in solution, with a large amount of deionization
Water is diluted and is centrifuged until neutrality is presented in filtrate pH value；Neutral solution will be presented with the filter paper filtering in 0.5 μm of aperture, with 80 DEG C
Lower baking is taken out after rs for 24 hours, and graphite oxide powder is obtained after grinding with agate mortar；The graphite oxide prepared is put into again
It in cast high temperature furnace, first carries out vacuumizing 5 minutes, then be passed through argon gas 30 minutes, be influenced with preventing external air from entering
Journey is that 60 DEG C/min is warming up to 1100 DEG C with heating rate, holds temperature one hour, when being heated up, be continually fed into argon gas
100sccm when reaching target temperature, is then passed through hydrogen 20sccm again, increases reduction effect, oxidable graphite thermal is removed and is made
Graphene.
Another aspect of the present invention also provides a kind of composite Nano graphite thermal phase-change material, and the composition of the material includes: stone
Wax, the paraffin are or mixtures thereof alkane derivative, form 80%~95% for the weight of the material, molecular formula Cn
H2n+2, wherein n=15~40；Composite Nano graphite forms 20%~5% for the weight of the material, the composite Nano graphite packet
Containing following composition: graphene, may include one of carbon nanotubes, expanded graphite, porous graphite, exfoliated graphite nano flake or
It is a variety of, 25%~65% is formed for the weight of the composite Nano graphite；Graphite oxide may include the stripping of graphite oxide, modification
One of copyable ink nano flake is a variety of, wherein modified exfoliated graphite nano flake be content of surface oxygen be 10% with
On exfoliated graphite nano flake；Wherein the paraffin can be one of cycloalkane, straight chain hydrocarbon compound or a variety of.
Preferably, wherein the expanded graphite by expansible graphite is passed through hydrogen at 1100 DEG C, through hot soarfing from being made.
Preferably, wherein the exfoliated graphite nano flake by expanded graphite after heat treated, shaken through ultrasonic vibrating
It is broken to be made.
Preferably, wherein the exfoliated graphite nano flake of the modification is the graphite flake of single-layer or multi-layer, with a thickness of 10
~100nm, the exfoliated graphite nano flake that content of surface oxygen is 10% or more.
Preferably, wherein the aqueous solution containing oxidant is heated to 80 DEG C by the exfoliated graphite nano flake of the modification, add
Enter exfoliated graphite nano flake after one is stirred to react, is made with aqueous solvent cleaning filtering.
Preferably, wherein the aqueous solvent of the exfoliated graphite nano flake of the modification is deionized water or pure water.
Preferably, wherein the exfoliated graphite nano flake of the modification is with aqueous solvent cleaning filtering until filtered water-soluble
Liquid pH value reaches neutral.
Preferably, wherein the aqueous solution for containing oxidant is acidic aqueous solution, neutral aqueous solution or alkaline aqueous solution.
Preferably, wherein the acidic aqueous solution is one of sulfuric acid, nitric acid, hydrochloric acid or a variety of.
Preferably, wherein the alkaline aqueous solution is one of potassium hydroxide, sodium hydroxide, potassium chloride or a variety of.
Preferably, wherein the neutral aqueous solution is potassinm permanganate aqueous solution.
Preferably, wherein the composite Nano graphite is graphite oxide/graphene/peeling nanometer of weight ratio 10:1:10
Graphite flake.
Preferably, wherein the composite Nano graphite is graphite oxide/graphene/peeling nanometer of weight ratio 20:1:10
Graphite flake.
Preferably, wherein the composite Nano graphite is graphite oxide/graphene/peeling nanometer of weight ratio 10:1:20
Graphite flake.
Compared with the prior art, composite Nano graphite thermal phase-change material proposed by the present invention has high thermal conductivity, high solidifying character
And high resistivity, it is able to the thermal interfacial material applied to electronic building brick heat-radiating substrate
Detailed description of the invention
Fig. 1 is one embodiment of the invention composite Nano graphite thermal phase-change material composition schematic diagram.
Fig. 2 is another embodiment of the present invention composite Nano graphite thermal phase-change material composition schematic diagram.
[main appended drawing reference]
11 ... paraffin
12 ... graphite oxides
13 ... graphenes
14 ... peel off nano graphite sheet
15 ... composite Nano graphite thermal phase-change materials
21 ... paraffin
22 ... graphenes
23 ... modified peeling nano graphite sheets
24 ... composite Nano graphite thermal phase-change materials
Specific embodiment
Technical solution of the present invention is further described in detail below in conjunction with attached drawing.
Embodiment one: the preparation of graphene (GE)
Uniform stirring in the mixed solution of sulfuric acid and nitric acid is added in 5g natural graphite powder (Graphite), then is slowly added
Enter 55g potassium chlorate.After mixed liquor stirs 96 hours at room temperature, repeats that 5% hydrochloric acid solution is added and be centrifuged, until solution
In there is no any sulfate ion, dilute and is centrifuged until neutrality is presented in filtrate pH value with a large amount of deionized water.To be in
Existing neutral solution is with the filter paper filtering in 0.5 μm of aperture, to take out after toasting rs for 24 hours at 80 DEG C, after being ground with agate mortar
To graphite oxide (GO) powder.The graphite oxide prepared (GO) is put into cast high temperature furnace again, first carries out vacuumizing 5 points
Clock, then it is passed through argon gas 30 minutes, it is 60 DEG C/min heating with heating rate to prevent external air from entering and influence process
To 1100 DEG C, temperature is held one hour, when being heated up, be continually fed into argon gas 100sccm, when reaching target temperature, be then passed through hydrogen again
Gas 20sccm increases reduction effect, by oxidable graphite (GO) hot soarfing from obtained graphene (GE).
Embodiment two: exfoliated graphite thin slice (xGnP) and modified exfoliated graphite preparation of sections (M-xGnP)
It takes the expansible graphite of 5g to be put into cast high temperature furnace, first carries out vacuumizing 5 minutes, then be passed through argon gas 30 minutes,
To prevent external air from entering and influence process, it is that 60 DEG C/min is warming up to 1100 DEG C with heating rate, holds temperature one hour, into
When row heating, it is continually fed into argon gas 100sccm, when reaching target temperature, then hydrogen 20sccm is passed through again, increases reduction effect,
By expansible graphite hot soarfing from obtained expanded graphite (EG).Acetone soln is added in expanded graphite (EG) after will be heat treated, sets
Enter and carry out within ultrasonic vibrating slot two hours shatter, obtained exfoliated graphite nano flake (xGnP), then configuration proportion is 3:1's
Sulfuric acid, nitric acid mixed liquor 400ml are heated to addition 10g exfoliated graphite nano flake (xGnP) after temperature is 80 DEG C and are stirred,
It is added in the deionized water of 5L and filters after agitated reaction, repetition filter action reaches neutral until pH value, obtains modification
Exfoliated graphite thin slice (M-xGnP).
Embodiment three: the preparation of composite Nano graphite thermal phase-change material
Taking 60g paraffin first, temperature of heating plate is set as 80 DEG C, and its is paraffin melting, pour into 200ml toluene and paraffin
It dissolves each other.It is slowly added into composite Nano graphite material, graphite oxide (GO)/graphene (GE)/peeling nano graphite sheet (xGnP)
Three-phase composite material carries out ultrasonic vibrating 30 minutes and then the composite Nano graphite material of shatter aggregation with 100W, and ensures
Can evenly dispersed nanofiller, then persistently stir one hour, gained mixture is poured into steel disk, and heat in exhausting cabinet
Solvent is evaporated to 130 DEG C, be subsequently poured into mold into mould and is put into baking oven rs catches up with remaining unevaporated toluene solution for 24 hours
It walks.The wherein composite Nano graphite material, graphite oxide (GO)/graphene (GE)/peeling nano graphite sheet (xGnP) three-phase
The weight ratio of composite material is added in above-mentioned paraffin solution with 10:1:10,20:1:10 and 10:1:20 respectively.
Since addition carbon materials are in paraffin composite material, other than it will increase its thermal conductivity, electric conductivity also can and then increase,
When the carbon materials content of filling reaches some quantity, conducting particles forms network because contacting with each other and reaches percolation threshold
(Percolation Threshold) makes entire composite material resistance value decline to a great extent.The hot maximum advantage of phase-change material is benefit
It is had with it in phase transition and largely inhales exothermic effect.It, can be by the energy storage in material when phase transformation material absorbs thermal energy
In material, but the speed that phase transition occurs, pyroconductivity also account for critically important status.Such as: when hot phase-change material start from
When centre receives thermal energy, if pyroconductivity is not high, the point that hot phase-change material contacts heat source at first can not can rapidly be passed hot
To other positions, instead, if heat transfer number is high, each section of hot phase-change material can be quickly delivered thermal energy to, is uniformly divided
Heat radiation energy effectively plays the function of hot phase-change material.The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to
It limits the scope of protection of the present invention.It is all in the spirit and principles in the present invention, made any modification and changes equivalent replacement
Into etc., it should be included in the interior of protection scope of the present invention.
Claims (1)
1. a kind of preparation method of graphene, comprising: 5g natural graphite powder to be added in the mixed solution of sulfuric acid and nitric acid
Even stirring is slow added into 55g potassium chlorate；After mixed liquor stirs 96 hours at room temperature, repeats 5% hydrochloric acid solution of addition and go forward side by side
Row centrifugation, until not having any sulfate ion to exist in solution, being diluted with a large amount of deionized water and being centrifuged until filtrate pH
Value presents neutral；Neutral solution will be presented with the filter paper filtering in 0.5 μm of aperture, to take out after toasting rs for 24 hours at 80 DEG C, with Ma
Graphite oxide powder is obtained after Nao mortar grinder；The graphite oxide prepared is put into cast high temperature furnace again, first carries out taking out true
It is 5 minutes empty, then it is passed through argon gas 30 minutes, to prevent external air from entering and influence process, with heating rate for 60 DEG C/min
1100 DEG C are warming up to, holds temperature one hour, when being heated up, argon gas 100sccm is continually fed into, when reaching target temperature, then leads to again
Enter hydrogen 20sccm, increase reduction effect, oxidable graphite thermal is removed, graphene is made.
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| CN201711188245.1A CN109835887A (en) | 2017-11-24 | 2017-11-24 | A kind of preparation method of graphene |
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| CN201711188245.1A CN109835887A (en) | 2017-11-24 | 2017-11-24 | A kind of preparation method of graphene |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112645311A (en) * | 2020-12-15 | 2021-04-13 | 浙江工业大学 | Method for preparing graphene by using hyperbranched polyethylene as auxiliary agent through ball milling method |
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2017
- 2017-11-24 CN CN201711188245.1A patent/CN109835887A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112645311A (en) * | 2020-12-15 | 2021-04-13 | 浙江工业大学 | Method for preparing graphene by using hyperbranched polyethylene as auxiliary agent through ball milling method |
| CN112645311B (en) * | 2020-12-15 | 2022-02-11 | 浙江工业大学 | Method for preparing graphene by using hyperbranched polyethylene as auxiliary agent through ball milling method |
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