CN106044755A - Method for preparing graphene by scanning graphite suspension mixed liquor through pulse lasers - Google Patents
Method for preparing graphene by scanning graphite suspension mixed liquor through pulse lasers Download PDFInfo
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- CN106044755A CN106044755A CN201610375347.3A CN201610375347A CN106044755A CN 106044755 A CN106044755 A CN 106044755A CN 201610375347 A CN201610375347 A CN 201610375347A CN 106044755 A CN106044755 A CN 106044755A
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- C01—INORGANIC CHEMISTRY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
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Abstract
The invention relates to a method for preparing graphene by scanning graphite suspension mixed liquor through pulse lasers. The method includes the steps that the graphite suspension mixed liquor is prepared, and evenly, continuously and circularly flows through a circulating pump, and the pulse lasers are focused under the liquid level to circularly scan the graphene suspension mixed liquor; the obtained supernatant is separated and dried with a gravity separating method, and the one-layer or few-layer (less than 6 layers) graphene with the complete structure and a smaller number of oxygen-containing functional groups is obtained. The graphene prepared with the method has good dispersing stability, and has excellent friction-reduction and anti-friction performance when serving as a lubricant additive. The method for preparing the graphene has the advantages of being simple in technology, short in preparing period, environmentally friendly, free of pollution, reliable in quality, capable of achieving continuous and large-scale production and the like. The new method is provided for large-scale, high-quality and structure-controllable preparing of the graphene.
Description
Technical field
The present invention relates to one utilize pulse laser to scan graphite suspension mixed solution under liquid level to prepare high-quality graphene
Method, belong to field of preparation of graphene.
Background technology
Graphene is a kind of New Two Dimensional planar carbon nano material being found for 2004, has with the connection of SP2 hydridization
Monoatomic layer structure, tightly packed one-tenth bi-dimensional cellular shape, have and enrich and the performance of uniqueness, it has also become get most of the attention in recent years
International research forward position and focus.In recent years, Graphene research mainly around magnanimity, controlled, the preparation of high-quality graphene and
Expanding Graphene applies two aspects to launch.
For realizing magnanimity, controlled, high-quality prepares Graphene, and research worker has successively developed micromechanics partition method, chemistry
Vapour deposition process, graphene oxide (GO) reducing process, the thermal decomposition technique such as SiC method, the direct stripping method of liquid phase, epitaxial growth method with
Technology, provides the foundation for realizing the controlled preparation of Graphene scale and the controlled modification of functionalization.For preparing graphene powder
For, the direct stripping method of liquid phase is most potential and development prospect a kind of preparation method.
The direct stripping method of liquid phase is first to process graphite with strong protonic acid, forms compound between graphite layers, adds strong oxidizer
Aoxidize, define graphene oxide, then with ultrasonic disperse to graphene oxide water solution to clearly without granule, add suitable
The oxygen-containing functional group on graphite oxide surface removed by the reducing agent of amount, through filtration, drying Graphene.Needed for the method, graphite is former
Expect inexpensive, be easy to get and preparation process is relatively easy, cost is relatively low, can prepare Graphene on a large scale, but stone prepared by the method
Ink alkene is reunited serious, and its electronic structure and perfection of crystal are affected by heavy damage, electronic property.It addition, in system
Employing substantial amounts of strong acid, strong oxidizer and strong reductant during Bei, this brings tired to follow-up waste water and waste liquid environmental protection treatment
Difficult.
Utilizing pulse laser the graphite that floats on a liquid is circulated scanning to prepare Graphene is a kind of new method, tool
Have that preparation technology is simple, the cycle is short, environment friendly and pollution-free, Graphene productivity high, the advantages such as oxygen-containing functional group is few on Graphene, can expire
Requirement the most extensive, that high-quality, structure-controllable prepare Graphene.
Summary of the invention
The technical problem to be solved is to provide a kind of pulse laser scanning graphite suspension and prepares high-quality stone
The method of ink alkene, and the material involved by the method and pulse laser scanning process.
The present invention is graphite, solvent and stabilizer to be mixed by a certain percentage, uses ultrasonic dispersion to obtain graphite and suspends
Mixed liquor, utilizes circulating pump to make graphite suspension mixed solution be circulated；Pulse laser is focused under liquid level, then enters
The continuous scan round of row；The supernatant of the graphite suspension mixed solution after utilizing gravitational separation process to scan pulse laser is centrifuged
And dried, high-quality Graphene can be obtained.
Specifically, a kind of side utilizing pulse laser scanning graphite suspension mixed solution to prepare Graphene that the present invention provides
Method, comprises the steps of:
(1) graphite, solvent and stabilizer are mixed with graphite suspension mixed solution；
(2) circulating pump is used to make step (1) gained graphite suspension mixed solution uniformly continuous circulate；
(3) pulse laser of pulse laser is focused under the liquid surface of graphite suspension mixed solution, scan round stone
Ink suspension mixed solution；
(4) supernatant of the graphite suspension mixed solution after scanning pulse laser is centrifuged separating, and gained precipitate exists
Vacuum drying oven is dried, it is thus achieved that Graphene.
Described graphite is crystalline flake graphite, and its structure is ABABAB ..., particle diameter 180 μm～300 μm, fixed carbon C content is big
In 94%, graphite mass fraction in graphite suspension mixed solution is 5.0%～30%.
In the inventive method, step (1) described solvent is the mixture of water and organic solvent, and wherein organic solvent is second
Alcohol, propylene glycol, n-butyl alcohol, acetone, ether, n-butyl ether, hexamethylene, the one of toluene or two kinds, control organic solvent and hang at this
Mass fraction in floating mixed liquor is 2.0%～20%.
Step (1) described stabilizer is Polyethylene Glycol, dodecyl sodium sulfate, oleic acid, 18-amine., lauryl sulphate acid
Sodium, γ-glycidyl ether oxygen propyl trimethoxy silicane (KH560) and γ-methacryloxypropyl trimethoxy silane
(KH570) one or two kinds, controlling stabilizer mass fraction in graphite suspension mixed solution is 0.5%～3.0%.
In step (2), circulation flow rate is 0.2mm/s～2.5mm/s.
In the inventive method, step (3) described pulse laser is solid state laser, optical maser wavelength is 335nm, 632nm,
One in 980nm or 1064nm.
The repetition rate of pulse laser that step (3) the described pulse laser scanning of the inventive method uses be 0.5～
15kHz, laser pulse width are 20～100ns, and output is 50～600W, and spot size is 3mm × 3mm～6mm × 6mm, swash
Photoscanning speed 2.0～15cm/s.
Pulse laser focusing described in step (3) is under liquid surface between 0.5mm～3.0mm.
Between the scan line speed 3～20mm/s of the scan round described in step (3), sweep time is at 10min～60min
Between.
The supernatant to the graphite suspension mixed solution after pulse laser scanning described in step (4) is centrifuged when separating
Centrifugal speed is between 2500～3500 revs/min, and centrifugation time is between 5min～30min, and gained precipitate is vacuum dried
Time vacuum between 0.01MPa～0.06MPa, temperature is between 70 DEG C～90 DEG C, between drying time 0.5h～3h.
The Graphene that said method of the present invention prepares falls within protection scope of the present invention.Prepare by the inventive method
Graphene be monolayer or few layer (less than 6 layers) Graphene, the structural integrity of Graphene, oxygen-containing functional group is few, and has good
Dispersive property.
The invention provides Graphene prepared by said method as lube oil additive application in terms of antifriction antiwear.
The core of the present invention is to solve two key technical problems:
One is the design and optimization of graphite suspension mixed solution.Pulse laser scan round graphite suspension mixed solution is used to prepare
Graphene must solve high-quality and the technological difficulties of high yield productivity of Graphene.Solve one of key of the two technological difficulties
It it is the Design and optimization of graphite suspension mixed solution.The graphite suspension mixed solution of the present invention is crystalline flake graphite+mixed solvent+stabilizer.
Two is the optimization of pulse laser scanning process parameter.Pulse laser scanning process is the skill obtaining high-quality graphene
One of art is crucial.Pulsed laser power is too high, and scanning speed is the slowest, and the energy that the graphite being suspended in mixed solution absorbs can mistake
Height, causes graphite gasification or plasma, generates other carbon nano-particles, it is impossible to obtain a large amount of high-quality Graphene；Pulse
Laser power is too low, and scanning speed is too fast, the little energy that the graphite in the solution that suspends absorbs, and graphite surface temperature is low, it is impossible to
Making graphite produce hole and impact phenomenon with water termination, the peeling effect of the graphite in the solution that suspends will be poor, it is impossible to generates
High yield and high-quality Graphene.
By laboratory observation, add a certain amount of mixed solvent and stabilizer in deionized water, by the technique of the present invention
Parameter scanning graphite suspension mixed solution can obtain the few monolayer of structural integrity, oxygen-containing functional group or few layer (less than 6 layers) Graphene,
And there is good dispersive property and properties of antifriction and wear resistance.
The present invention provide the process flow diagram preparing Graphene as shown in Figure 1:
The inventive method has a following remarkable result:
(1) be easy to get by raw material, crystalline flake graphite that price is low is converted into new carbon Graphene.
(2) pulse laser scanning graphite suspension mixed solution prepares the features simple and practical process of Graphene, and manufacturing cycle is short, gained
The structural integrity of Graphene, reliable in quality, there is good dispersive property.
(3) not using strong oxidizer, strong reductant, waste water and waste liquid during the inventive method, environmental pollution is little, easily
Carry out environmental protection treatment.
(4) present invention is extensive, high-quality, contamination-freely prepares the Graphene that compound with regular structure, thickness and size are controlled
Provide new method.
Accompanying drawing explanation
Fig. 1 is transmitted electron Electronic Speculum (TEM) figure of the Graphene sample of the embodiment of the present invention 1 preparation.
Fig. 2 A is atomic force microscope (AFM) figure of the Graphene of the embodiment of the present invention 1 preparation, and Fig. 2 B is corresponding diagram 2A
Cross-section analysis figure.
Fig. 3 A is the electron diffraction pattern figure of the Graphene of the embodiment of the present invention 2 preparation, and Fig. 3 B is the stone of embodiment 2 preparation
Ink alkene height explanation transmitted electron Electronic Speculum (HRTEM) figure.
Scanning electron microscope (SEM) figure of worn-out surface after oil drag test based on Fig. 4 A, Fig. 4 B is to add 0.05Wt%
Scanning electron microscope (SEM) figure of worn-out surface after the Graphene friction test of the embodiment of the present invention 2 preparation.
Detailed description of the invention
The example of the present invention will be further illustrated pulse laser scanning deflocculated graphite liquid and prepares method concrete of Graphene
Embodiment, but the invention is not limited in subordinate's embodiment.
If not specializing, chemical reagent used in embodiment is conventional commercial reagent, skill used in embodiment
The conventional means that art means are well known to those skilled in the art.
Embodiment 1
Step 1: the preparation of graphite suspension mixed solution.50mL ethanol, 6g dodecyl sodium sulfate are separately added into 500mL's
In deionized water, after stirring, add 100g crystalline flake graphite, ultrasonic disperse 10min.
Step 2: ON cycle pump, coutroi velocity is 0.5mm/s, makes graphite suspension mixed solution start the cycle over.
Step 3: pulse laser scans.Locating pulse laser under liquid level 1.0mm to focus on, pulse laser wavelength is
1064nm, repetition rate is 5kHz, laser pulse width is 50ns, and output is 300W, and spot size is 5mm × 5mm, scanning speed
Degree is 8cm/s.
Step 4: separate and collect, it is thus achieved that Graphene.After laser scanning 20min, utilize gravitational separation process to collect graphite and hang
The supernatant of floating mixed liquor.First centrifugation supernatant, centrifugation time 15min, rotating speed: 3000r/min, by bottom sediment
Collect, and at 0.05PMa, temperature 80 DEG C, be dried 30min, the few layer graphene being easily dispersed can be obtained.
Graphene prepared by the method can obtain concentration, and to be about the uniform and stable Graphene of 1.5mg/mL water-dispersible
System.
Fig. 1 is the transmission electron microscope (TEM) of Graphene sample prepared by the present embodiment, it can be seen that prepared by the present embodiment
Graphene has a large amount of fold and rises and falls and slightly crimp, and the existence of its fold makes the free energy of Graphene system reduce, stability
Increase.By contrasting at comparison of light and shade in image and fold, Graphene thickness prepared by the present embodiment can be deduced about
For few layer graphene.In order to further characterize the thickness of Graphene, under atomic force microscope (AFM), observe the present embodiment obtain
Graphene, as in figure 2 it is shown, in this viewing area, the thickness of Graphene is about 1.5nm～5.0nm.Wherein, a carbon
Atomic layer level thickness is 0.35nm, and in graphite, graphene film interlamellar spacing is 0.335nm, and bottom graphene film and base (silicon chip)
Between there is the space of 0.5nm～0.8nm, thus infer that the thickness of Graphene prepared by the present embodiment is about 1～5 layer.
Embodiment 2
Step 1: prepared by the mixed solution of graphitiferous.50mL ethanol is added together with 25mL hexamethylene 500mL go from
In sub-water, after stirring, it is separately added into 10g oleic acid and 150g crystalline flake graphite, ultrasonic disperse 10min.
Step 2: ON cycle pump, coutroi velocity is 1.0m/s, makes graphite suspension mixed solution start the cycle over.
Step 3: pulse laser scans.Locating pulse laser under liquid level 1.2mm to focus on, the wavelength of pulse laser is
335nm, repetition rate is 8kHz, laser pulse width is 80ns, and output is 200W, and spot size is 5mm × 5mm, scanning speed
Degree is 6cm/s.
Step 4: separate and collect, it is thus achieved that Graphene.After laser scanning 10min, utilize gravitational separation process to collect graphite and hang
The supernatant of floating mixed liquor, by the supernatant of collection centrifugation 5min under rotating speed is 4000r/min.Centrifugation is obtained
Solids at 0.5 atmospheric pressure, temperature 80 DEG C be dried 30min, the Graphene of few layer be easily dispersed can be obtained.
Fig. 3 is electron diffraction pattern and the HRTEM image of Graphene prepared by the present embodiment, it can be seen that the electricity of Graphene
Sub-diffraction pattern is typical hexagonal features, and this is identical with the diffraction pattern of the Graphene having good crystal formation and Graphene,
For the basic framework of Graphene, and calculate through software analysis that to obtain graphene layer spacing be 0.38nm, a carbon atomic layer thickness
For 0.35nm, Graphene is 3-4 layer.
MFT-R4000 type multi-functional reciprocating friction Wear Tester is investigated the Graphene of embodiment 2 acquisition as profit
The anti-wear and wear-resistant performance of oil additive.Base oil is liquid paraffin, and the addition of Graphene is 0.05Wt%, and friction pair is
GCr15 ball/45 steel, experimental condition is: frequency 5Hz, load 20N, friction stroke 10mm, test period 30min.
At the conditions of the experiments described above, the coefficient of friction of base oil is 0.11, and wear volume is 7.0 × 106 μm 3, and adds
Coefficient of friction after Graphene be 0.04 wear volume be 4.55 × 106 μm 3, compare with base oil, frictional decrease
64%；Wear volume have dropped 35%.
Worn-out surface after the Graphene friction test that based on Fig. 4 prepared by the embodiment of the present invention of oil and interpolation 0.05Wt%
Scanning electron microscope (SEM) figure, it can be seen that after the lower friction test of base oil lubrication, wear surface is the most rough, exists a large amount of
Width and deep ditch dug with a plow, and after adding Graphene, wear surface becomes smooth, and without obvious ditch dug with a plow, this illustrates Graphene conduct
Lube oil additive has the anti-wear performance of excellence.
Claims (10)
1. one kind utilizes the method that pulse laser scanning graphite suspension mixed solution prepares Graphene, it is characterised in that: comprise as follows
Step:
(1) graphite, solvent and stabilizer are mixed with graphite suspension mixed solution；
(2) circulating pump is used to make step (1) gained graphite suspension mixed solution uniformly continuous circulate；
(3) pulse laser that pulse laser produces is focused under the liquid surface of graphite suspension mixed solution, scan round stone
Ink suspension mixed solution；
(4) supernatant of the graphite suspension mixed solution after scanning pulse laser is centrifuged separating, and gained precipitate is in vacuum
Drying baker is dried, it is thus achieved that Graphene.
Method the most according to claim 1, it is characterised in that: described graphite is crystalline flake graphite, and particle diameter is 180 μm～300 μ
M, fixed carbon C content is more than 94%, and graphite mass fraction in graphite suspension mixed solution is 5.0%～30%.
Method the most according to claim 1, it is characterised in that: described solvent is the mixture of water and organic solvent, wherein
Organic solvent is ethanol, propylene glycol, n-butyl alcohol, acetone, ether, n-butyl ether, hexamethylene, the one of toluene or two kinds, controls to have
Machine solvent mass fraction in graphite suspension mixed solution is 2.0%～20%.
Method the most according to claim 1, it is characterised in that: stabilizer is Polyethylene Glycol, dodecyl sodium sulfate, oil
Acid, 18-amine., sodium lauryl sulphate, γ-glycidyl ether oxygen propyl trimethoxy silicane and γ-methacryloxy third
The one of base trimethoxy silane or two kinds, control stabilizer mass fraction in graphite suspension mixed solution be 0.5%～
3.0%.
Method the most according to claim 1, it is characterised in that: step (3) described pulse laser is solid state laser, swashs
One in light wave a length of 335nm, 632nm, 980nm or 1064nm.
6. according to the arbitrary described method of claim 1-5, it is characterised in that: the pulse laser that the scanning of described pulse laser uses
Repetition rate be 0.5～15kHz, laser pulse width be 20～100ns, output is 50～600W, spot size be 3mm ×
3mm～6mm × 6mm, laser scanning speed 2.0～15cm/s.
7. according to the arbitrary described method of claim 1-5, it is characterised in that: the pulse laser focusing described in step (3) is at liquid
0.5mm～3.0mm under surface.
8. according to the arbitrary described method of claim 1-5, it is characterised in that: the scan line of the scan round described in step (3)
Speed is 3～20mm/s, sweep time 10min～60min.
9. according to the arbitrary described method of claim 1-5, it is characterised in that: after pulse laser is scanned described in step (4)
The centrifugal speed that is centrifuged when separating of the supernatant of graphite suspension mixed solution be 2500～3500 revs/min, centrifugation time
5min～30min, the vacuum 0.01MPa during vacuum drying of gained precipitate～0.06MPa, temperature 70 C～90 DEG C, it is dried
Time 0.5h～3h.
10. the Graphene that claim 1-9 either method prepares.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107032333A (en) * | 2017-06-15 | 2017-08-11 | 成都新柯力化工科技有限公司 | A kind of method that graphene is prepared based on laser lift-off |
| CN108133830A (en) * | 2017-12-27 | 2018-06-08 | 济南大学 | A kind of preparation method of graphene/ultramicro active charcoal Particles dispersed electrode material |
| CN111470498A (en) * | 2019-10-15 | 2020-07-31 | 中山大学 | Preparation method and application of water-phase graphene |
| CN113232737A (en) * | 2021-06-03 | 2021-08-10 | 吉林大学 | Insect robot with super-smooth surface, processing method and application |
| CN115321528A (en) * | 2022-09-21 | 2022-11-11 | 亚太中碳(山西)新材料科技有限公司 | Continuous preparation method of graphene material |
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| CN107032333A (en) * | 2017-06-15 | 2017-08-11 | 成都新柯力化工科技有限公司 | A kind of method that graphene is prepared based on laser lift-off |
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| CN108133830B (en) * | 2017-12-27 | 2019-12-03 | 济南大学 | A kind of preparation method of graphene/ultramicro active charcoal Particles dispersed electrode material |
| CN111470498A (en) * | 2019-10-15 | 2020-07-31 | 中山大学 | Preparation method and application of water-phase graphene |
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| CN115321528B (en) * | 2022-09-21 | 2024-01-02 | 亚太中碳(山西)新材料科技有限公司 | Continuous preparation method of graphene material |
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