CN105836737B - A method of it is combined with jet stream stripping using ultrasound stripping and prepares graphene - Google Patents
A method of it is combined with jet stream stripping using ultrasound stripping and prepares graphene Download PDFInfo
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- CN105836737B CN105836737B CN201610296912.7A CN201610296912A CN105836737B CN 105836737 B CN105836737 B CN 105836737B CN 201610296912 A CN201610296912 A CN 201610296912A CN 105836737 B CN105836737 B CN 105836737B
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- C01—INORGANIC CHEMISTRY
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- C01P2002/00—Crystal-structural characteristics
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract
The method preparing graphene is combined with jet stream stripping using ultrasound stripping the invention discloses a kind of, including：(1) by graphite dispersion in aqueous surfactant solution；(2) mixed liquor for obtaining step (1) carries out ultrasonic stripping, obtains multi-layer graphene dispersion liquid；(3) the multi-layer graphene dispersion liquid for obtaining step (2) carries out jet stream stripping, obtains single-layer graphene dispersion liquid；(4) processing is dried in the single-layer graphene dispersion liquid that step (3) obtains, graphene is made.The stripping mode that the preparation method of the present invention is combined using ultrasound with jet stream for the first time, graphene-structured defect is few in the dispersion liquid being prepared, the number of plies is few, concentration is high, and the excellent properties of graphene are remained well, it can be widely applied to the fields such as auto parts and components, sensor, conductive material, Heat Conduction Material.The method of the present invention is economic and environment-friendly, not only improves raw material availability, but also reduces industrialization cost.
Description
Technical field
The invention belongs to graphene functional material preparing technical fields, and in particular to a kind of to be shelled with jet stream using ultrasound stripping
From being combined the method for preparing graphene.
Technical background
Since the strong seas K nurse of the peace moral of Univ Manchester UK (Andre K.Geim) etc. prepared stone in 2004
Black alkene material, since its unique structure and photoelectric property receive people and widely pay attention to.Graphene is by one layer of carbon atom
The two-dimentional carbon nanomaterial of composition is to be currently known most thin two-dimensional material, and thickness is only 0.34nm.Mono-layer graphite is big due to it
Specific surface area, excellent conduction, heat conductivility and low coefficient of thermal expansion and be considered as ideal material.It can be in macromolecule
It is used widely in the fields such as material, ultracapacitor, fiber, electrode material, electronics.
The preparation method of graphene has mechanical stripping method, ultrahigh vacuum graphene epitaxial growth method, chemical vapor deposition at present
Area method, oxidation-reduction method, electrolysis, ultrasonic stripping method, solvent-thermal method etc..The graphene quality that wherein prepared by mechanical stripping method
Highest, but its yield is very low, is only used for scientific research；The high cost and roundlet of ultrahigh vacuum graphene epitaxial growth method
The structure of piece limits its application；Chemical vapor deposition and graphene defect prepared by epitaxial growth method are few, but are wanted to equipment
Ask high, feed stock conversion is low, significantly limits its application；It can the large-scale production number of plies although oxidation-reduction method prepares graphene
Less graphene, but strong oxidizer makes its hexagonal honeycomb crystal structure that can not restore the destruction of graphene lattice, causes
Its partial properties lacks；Electrolysis can synthesize a large amount of graphene, but the surface of the graphene synthesized carries largely
Cation or anion or organic matter；Ultrasonic stripping method is using graphite or expanded graphite as raw material, and equipment requirement is low, and low energy consumption, and
The graphene defect of preparation is few, and concentration is high, it is considered to be a kind of most promising preparation method；The graphene of hot solvent method synthesis
Purity is higher, but the reaction time is relatively long, and yield only has 1~5%.
Invention content
It is mutually tied using ultrasound stripping and jet stream stripping it is an object of the invention to overcome the deficiencies of the prior art and provide a kind of
The method that conjunction prepares graphene.The stripping mode that the preparation method of the present invention is combined using ultrasound with jet stream for the first time, is prepared into
To dispersion liquid in graphene-structured defect it is few, the number of plies is few, and concentration is high, and remains the excellent properties of graphene well, can
It is widely used in the fields such as auto parts and components, sensor, conductive material, Heat Conduction Material.The method of the present invention is economic and environment-friendly, both improves
Raw material availability, and reduce industrialization cost.
The purpose of the present invention is achieved through the following technical solutions：
The method preparing graphene is combined with jet stream stripping using ultrasound stripping the purpose of the present invention is to provide a kind of,
Including：
(1) by graphite dispersion in aqueous surfactant solution；
(2) mixed liquor for obtaining step (1) carries out ultrasonic stripping, obtains graphene dispersing solution I, i.e. multi-layer graphene point
Dispersion liquid；
(3) graphene dispersing solution I (multi-layer graphene dispersion liquid) obtained step (2) carries out jet stream stripping, obtains stone
Black alkene dispersion liquid II, i.e. single-layer graphene dispersion liquid；
(4) processing is dried in the graphene dispersing solution II (single-layer graphene dispersion liquid) that step (3) obtains, stone is made
Black alkene product.
Further, the purity of graphite is 99.90wt%~99.95wt%, median particle diameter (D50) in the step (1)
It is 10~100 μm.
Further, surfactant is selected from neopelex, cetyl trimethyl bromine in the step (1)
Change one or more of ammonium, lauryl sodium sulfate, sodium lignin sulfonate.
Further, the mass concentration of aqueous surfactant solution is 0.5~5.0g/L in the step (1).
Further, the mass concentration of graphite is 25~75g/L in the step (1).
Further, the power of ultrasound stripping is 300~1000W in the step (2), and the time is 6~12 hours.
Further, the quality of graphene is dense in graphene dispersing solution I (multi-layer graphene dispersion liquid) in the step (2)
Degree is 25~75g/L.
Further, in the step (3) jet stream remove flow velocity be 300~400L/h, 2~4bar of feed pump pressure,
60 DEG C, 300~1000bar of nozzle exit pressure of drop temperature <, cycle-index 4~8 times.
Further, vacuum drying temperature is 80~100 DEG C in the step (4), and the time is 3~6 hours.
Compared with prior art, the positive effect of the present invention is as follows：
The preparation method cost of the present invention is relatively low, preparation method of purity and the higher graphene of yield.It the advantage is that：
(1) preparation method of the invention using graphite as raw material, it is cheap at low cost, it is more easily peelable at graphite
Alkene, and it is greatly improved yield；
(2) water and surfactant is used to remove reagent as intercalation, it is safer, environmentally friendly and environmental-friendly；
(3) preparation method is simple to equipment requirement, easy to operate, and production stage is few, is suitable for mass producing.
(4) the graphene-structured defect that preparation method using the present invention obtains is few, and the number of plies is few, and concentration is high, and well
Remain the excellent properties of graphene.
Description of the drawings
Fig. 1 is ultrasonic stripping off device schematic diagram.
Fig. 2 is jet stream stripping off device schematic diagram.
Fig. 3 is single ultrasonic lift-off processing technique TEM collection of illustrative plates.
Fig. 4 is single jet stream lift-off processing technique TEM collection of illustrative plates.
Fig. 5 is the TEM collection of illustrative plates of graphene prepared by embodiment 5.
Fig. 6 is the XRD diagram spectrum analysis of black alkene prepared by embodiment 5.
Specific implementation mode
With reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.
Fig. 1 is ultrasonic stripping off device schematic diagram, and the material in mixing plant is delivered to by peristaltic pump in ultrasonic device,
It is back in mixing plant after being removed by ultrasound, by cycle until getting a desired effect, is mainly controlled in the technological process
The power and ultrasonic time of ultrasonic device processed；
Fig. 2 is jet stream stripping off device schematic diagram, and material is delivered to through diaphragm pump at nozzle, is penetrated after high-pressure at nozzle
It flow in cavity, is exported after cavity is filtered under diminished pressure and be back to charging basket, main coutroi velocity, charging pump pressure in the technological process
Power, discharge port temperature, nozzle exit pressure and cycle-index.
Graphite raw material in following embodiment is bought from tsingtauite sea carbon material Co., Ltd.
Embodiment 1
1,0.5g/L sodium dodecyl benzene sulfonate aqueous solutions, high-speed stirred 30 minutes are prepared；
2, it is 99.90wt% by purity, the graphite that median particle diameter (D50) is 10 μm is added to the detergent alkylate of step 1
In sulfonic acid sodium water solution, graphite concentration 25g/L, high-speed stirred 30 minutes；
3, Fig. 1 ultrasound stripping off device schematic diagrames are pressed and carry out ultrasonic stripping, wherein ultrasonic power is 300W, ultrasonic time 12
Hour；
4, Fig. 2 jet stream stripping off device schematic diagrames are pressed and carry out jet stream stripping, wherein flow velocity is 300L/h, and feed pump pressure is
2bar, discharge port temperature are 56 DEG C, nozzle exit pressure 300bar, and cycle-index is 8 times；
5, vacuum drying obtains graphene, and wherein drying temperature is 80 DEG C, drying time 6h.
Embodiment 2
1,1.0g/L cetyl trimethylammonium bromide aqueous solutions, high-speed stirred 30 minutes are prepared；
2, it is 99.90wt% by purity, the graphite that median particle diameter (D50) is 60 μm is added to the cetyl three of step 1
In methyl bromide aqueous ammonium, graphite concentration 50g/L, high-speed stirred 30 minutes；
3, Fig. 1 ultrasound stripping off device schematic diagrames are pressed and carry out ultrasonic stripping, wherein ultrasonic power is 500W, ultrasonic time 10
Hour；
4, Fig. 2 jet stream stripping off device schematic diagrames are pressed and carry out jet stream stripping, wherein flow velocity is 350L/h, and feed pump pressure is
3bar, discharge port temperature are 58 DEG C, nozzle exit pressure 500bar, and cycle-index is 7 times；
5, vacuum drying obtains graphene, and wherein drying temperature is 80 DEG C, drying time 6h.
Embodiment 3
1,2.0g/L lauryl sodium sulfate aqueous solutions, high-speed stirred 30 minutes are prepared；
2, it is 99.95wt% by purity, the graphite that median particle diameter (D50) is 50 μm is added to the dodecyl sulphur of step 1
In acid sodium aqueous solution, graphite concentration 50g/L, high-speed stirred 30 minutes；
3, Fig. 1 ultrasound stripping off device schematic diagrames are pressed and carry out ultrasonic stripping, wherein ultrasonic power is 750W, ultrasonic time 8
Hour；
4, Fig. 2 jet stream stripping off device schematic diagrames are pressed and carry out jet stream stripping, wherein flow velocity is 350L/h, and feed pump pressure is
3bar, discharge port temperature are 57 DEG C, nozzle exit pressure 700bar, and cycle-index is 5 times；
5, vacuum drying obtains graphene, and wherein drying temperature is 80 DEG C, drying time 5h.
Embodiment 4
1,3.0g/L lignin sulfonic acid sodium water solutions, high-speed stirred 30 minutes are prepared；
2, it is 99.95wt% by purity, the graphite that median particle diameter (D50) is 80 μm is added to the lignin sulfonic acid of step 1
In sodium water solution, graphite concentration 75g/L, high-speed stirred 30 minutes；
3, Fig. 1 ultrasound stripping off device schematic diagrames are pressed and carry out ultrasonic stripping, wherein ultrasonic power is 800W, ultrasonic time 6
Hour；
4, Fig. 2 jet stream stripping off device schematic diagrames are pressed and carry out jet stream stripping, wherein flow velocity is 400L/h, and feed pump pressure is
4bar, discharge port temperature are 55 DEG C, nozzle exit pressure 1000bar, and cycle-index is 8 times；
5, vacuum drying obtains graphene, and wherein drying temperature is 100 DEG C, drying time 3h.
Embodiment 5
1,5.0g/L neopelexes and cetyl trimethylammonium bromide mixed aqueous solution (dodecyl are prepared
Benzene sulfonic acid sodium salt is 1 with cetyl trimethylammonium bromide mass ratio:1), high-speed stirred 30 minutes；
2, it is 99.95wt% by purity, the graphite that median particle diameter (D50) is 100 μm is added to the mixed aqueous solution of step 1
In, graphite concentration 75g/L, high-speed stirred 30 minutes；
3, Fig. 1 ultrasound stripping off device schematic diagrames are pressed and carry out ultrasonic stripping, wherein ultrasonic power is 1000W, and ultrasonic time is
10 hours；
4, Fig. 2 jet stream stripping off device schematic diagrames are pressed and carry out jet stream stripping, wherein flow velocity is 400L/h, and feed pump pressure is
4bar, discharge port temperature are 56 DEG C, nozzle exit pressure 1000bar, and cycle-index is 6 times；
5, vacuum drying obtains graphene, and wherein drying temperature is 100 DEG C, drying time 4h.
Comparative example 1
1,5.0g/L neopelexes and cetyl trimethylammonium bromide mixed aqueous solution (dodecyl are prepared
Benzene sulfonic acid sodium salt is 1 with cetyl trimethylammonium bromide mass ratio:1), high-speed stirred 30 minutes；
2, it is 99.95wt% by purity, the graphite that median particle diameter (D50) is 100 μm is added to the mixed aqueous solution of step 1
In, a concentration of 75g/L of graphite quality, high-speed stirred 30 minutes；
3, Fig. 1 ultrasound stripping off device schematic diagrames are pressed and carry out ultrasonic stripping, wherein ultrasonic power is 1000W, and ultrasonic time is
10 hours；
4, vacuum drying obtains graphene, and wherein drying temperature is 100 DEG C, drying time 4h.
Comparative example 2
1,5.0g/L neopelexes and cetyl trimethylammonium bromide mixed aqueous solution (dodecyl are prepared
Benzene sulfonic acid sodium salt is 1 with cetyl trimethylammonium bromide mass ratio:1), high-speed stirred 30 minutes；
2, it is 99.95wt% by purity, the graphite that median particle diameter (D50) is 100 μm is added to the mixed aqueous solution of step 1
In, a concentration of 75g/L of graphite quality, high-speed stirred 30 minutes；
3, Fig. 2 jet stream stripping off device schematic diagrames are pressed and carry out jet stream stripping, wherein flow velocity is 400L/h, and feed pump pressure is
4bar, discharge port temperature are 56 DEG C, nozzle exit pressure 1000bar, and cycle-index is 6 times；
4, vacuum drying obtains graphene, and wherein drying temperature is 100 DEG C, drying time 4h.
Fig. 5 and Fig. 6 are please referred to, the graphene TEM collection of illustrative plates and XRD diagram spectrum analysis of the preparation of embodiment 5 are shown.Compare comparison
Example 1 uses the graphite of single jet stream lift-off processing using the graphene TEM (such as Fig. 3) and comparative example 2 of single ultrasonic lift-off processing
Alkene TEM (such as Fig. 4), it can be seen that embodiment 5 can obtain the higher graphite ene product of purity, and the graphite ene product is with good
Good laminated structure.
Claims (6)
1. a kind of being combined the method for preparing graphene using ultrasound stripping with jet stream stripping, including：
(1) by graphite dispersion in aqueous surfactant solution；
(2) mixed liquor for obtaining step (1) carries out ultrasonic stripping, obtains graphene dispersing solution I；
(3) graphene dispersing solution I for obtaining step (2) carries out jet stream stripping, obtains graphene dispersing solution II；
(4) processing is dried in the graphene dispersing solution II that step (3) obtains, graphene is made,
Wherein, in step (1), the mass concentration of graphite is 25~75g/L, and surfactant is selected from dodecyl benzene sulfonic acid
Sodium, one or more of cetyl trimethylammonium bromide, lauryl sodium sulfate, sodium lignin sulfonate, surfactant
The mass concentration of aqueous solution is 0.5~5.0g/L.
2. a kind of removed with jet stream using ultrasound stripping according to claim 1 is combined the method for preparing graphene,
It is characterized in that：The purity of graphite is 99.90wt%~99.95wt% in the step (1), and median particle diameter D50 is 10~100 μ
m。
3. a kind of removed with jet stream using ultrasound stripping according to claim 1 is combined the method for preparing graphene,
It is characterized in that：The power of ultrasound stripping is 300~1000W in the step (2), and the time is 6~12 hours.
4. a kind of removed with jet stream using ultrasound stripping according to claim 1 is combined the method for preparing graphene,
It is characterized in that：The mass concentration of graphene is 25~75g/L in graphene dispersing solution I in the step (2).
5. a kind of removed with jet stream using ultrasound stripping according to claim 1 is combined the method for preparing graphene,
It is characterized in that：The flow velocity that jet stream is removed in the step (3) is 300~400L/h, 2~4bar of feed pump pressure, drop temperature
60 DEG C, 300~1000bar of nozzle exit pressure of <, cycle-index 4~8 times.
6. a kind of removed with jet stream using ultrasound stripping according to claim 1 is combined the method for preparing graphene,
It is characterized in that：Vacuum drying temperature is 80~100 DEG C in the step (4), and the time is 3~6 hours.
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| TWI668187B (en) * | 2016-10-07 | 2019-08-11 | 林逸樵 | Device for rapidly producing graphene and method thereof |
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Application publication date: 20160810 Assignee: Shanghai Li Sheng Nano Technology Co., Ltd. Assignor: Shanghai Co., Ltd of Li Wusheng enterprise group Contract record no.: X2019310000016 Denomination of invention: Method for preparing graphene by combining ultrasonic peeling and jet flow peeling Granted publication date: 20181109 License type: Exclusive License Record date: 20191015 |