CN102910624A - Preparation method of high-yield graphene without defects - Google Patents
Preparation method of high-yield graphene without defects Download PDFInfo
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- CN102910624A CN102910624A CN201210443498XA CN201210443498A CN102910624A CN 102910624 A CN102910624 A CN 102910624A CN 201210443498X A CN201210443498X A CN 201210443498XA CN 201210443498 A CN201210443498 A CN 201210443498A CN 102910624 A CN102910624 A CN 102910624A
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Abstract
The invention provides a preparation method of high-yield graphene without defects. The preparation method comprises the following steps of: adding graphite powder and organic salt into a solvent and mixing; performing ultrasonic processing on the mixture; centrifuging the mixture subjected to ultrasonic striping; removing graphite particles which are not stripped; and collecting a suspension liquid to obtain a dispersion liquid of the graphene without defect. According to the preparation method provided by the invention, the organic salt is added into the solvent to play a role in obviously enhancing the stripped graphite in the solvent in an assisting manner, the dispersion liquid of the graphene under different solvent systems can be prepared in situ, the concentration of the obtained dispersion liquid of the graphene is improved by multiple times to 102 times compared with that of a pure-solvent system, and the structure and composition of the stripped graphene do not have defects. The method provided by the invention is simple and easy to operate, the strong-oxidizing reagent is not involved, the power consumption is low, the aftertreatment is simple, and the yield of the graphene without defect can be increased obviously.
Description
Technical field
The invention belongs to the Graphene preparing technical field, relate to a kind of preparation method of Graphene, be specifically related to a kind ofly peel off graphite by direct liquid phase and come high yield to prepare the method for zero defect Graphene.
Background technology
2004, the physicist An Deliehaimu of Univ Manchester UK and Constantine Nuo Woxiaoluofu, but successfully from graphite, isolate the Two-dimensional Carbon material-Graphene of Individual existence by simple mechanically peel method, and its character measured and characterize, show the physicals that it is superior, thereby started the prelude of Graphene research.Therefore two scientists also obtain Nobel Prize in physics in 2010.As the soccerballene that continues, the carbon nanomaterial of up-to-date form after the carbon nanotube, Graphene is since being in the news, owing to have the physicochemical property of a series of novelties, such as ultrafast charge migration speed, huge specific surface area and the physical strength of superelevation etc. are widely used in the electrochemical field such as ultracapacitor, electrocatalysis.
But up to the present, the method for preparing Graphene is not perfect.Specifically, present method can't be prepared output and gratifying Graphene simultaneously qualitatively.Representative micromechanics stripping method and chemical Vapor deposition process can be prepared the pure Graphene of high quality, but output is too low, can't large-scale application; Though and the chemistry redox method of generally using can mass-producing prepare Graphene, but the gained Graphene inevitably with the defective on the structure and composition, thereby reduce its superior electric property.Hibernian Coleman seminar confirmed that flawless pure Graphene can directly be scattered in certain solvent by the ultrasonic graphite of peeling off in 2008.A large amount of preparation zero defect Graphenes that appear as of this direct liquid phase stripping method provide a feasible approach, peel off but the method for reporting at present is generally neat solvent, and output is generally on the low side, sees the following form 1.
The at present direct liquid phase of table 1 is peeled off the main achievement of preparation Graphene
Summary of the invention
The object of the present invention is to provide a kind of preparation method of high yield zero defect Graphene, it is a kind of efficient liquid phase lift-off technology, greatly strengthened the efficient of peeling off graphite in the common solvent by adding organic salt, peeled off graphite by direct liquid phase and come high yield to prepare the zero defect Graphene.
The technical solution adopted in the present invention is as follows:
A kind of preparation method of zero defect Graphene is characterized in that, will mix in Graphite Powder 99 and the organic salt adding solvent, and mixture carries out supersound process; Mixture after ultrasonic the peeling off is centrifugal, remove the unstripped graphite particle of opening, collect the dispersion liquid that suspension namely obtains the zero defect Graphene.
By adding common organic salt as efficient auxiliary in solvent, the applicant is surprised to find that the inventive method can greatly strengthen the efficient of peeling off graphite in the solvent, and peels off the graphene-structured that obtains and form upper zero defect.
The preferred chemical pure natural graphite powder of described Graphite Powder 99, particle diameter≤30 μ m.
Described organic salt is one or more in disodium ethylene diamine tetraacetate, sodium tartrate, Seignette salt, soluble tartrate, Trisodium Citrate or the Tripotassium Citrate.
Described solvent is that liquid phase is peeled off various common solvent in the preparation Graphene, such as chloroform, acetone, Virahol, n-propyl alcohol, pyridine, ethanol, ethyl acetate, dimethyl sulfoxide (DMSO) (DMSO), N, dinethylformamide (DMF), N-Methyl pyrrolidone (NMP) etc., preferred dimethyl sulfoxide (DMSO), DMF or N-Methyl pyrrolidone.
The starting point concentration of described graphite is 2～30 mg mL
-1, the starting point concentration of organic salt is 4～60 mg mL
-1
In the described method, the ultrasonic temperature of peeling off is room temperature (15～30 ℃), and the time is preferably 2-5 hour.
In the described method, centrifugal rotational speed is 3000 rpm, and centrifugation time is 40 min.
The preparation method of zero defect Graphene of the present invention, the organic salt that adds in the solvent, booster action by means of organic salt, gentleness ultrasonic with solvent action under graphite is directly peeled off into Graphene, and form stable graphene dispersing solution, but original position prepares the graphene dispersing solution under the different solvents system.Organic salt has significantly auxiliary reinforcing effect to peeling off graphite in the solvent, and the graphene dispersing solution concentration that obtains is compared with the neat solvent system and improved several times to 10
2Times, and peel off the graphene-structured that obtains and form upper zero defect.The inventive method is simple, does not relate to strong oxidizing property reagent, and it is low to consume energy, and toxicity is little, and aftertreatment is simple, and gained Graphene output is compared with the neat solvent system and is significantly improved.Peel off the method for preparing Graphene with neat solvent liquid phase in the prior art and compare, have the following advantages at least:
1. the employed reagent of the inventive method is nontoxic or low toxicity reagent, low price; The organic salt that adds is peeled off graphite to multi-solvents (comprising high boiling point and lower boiling solvent) and is all had wide effect and significantly assist reinforcing effect, but original position prepares the graphene dispersing solution under the different solvents system; Organic salt consumption is few, but and Reusability.
2. the ultrasonic splitting time of the inventive method is short, and it is low to consume energy, and preparation process is simple.
3. the Graphene output of the inventive method preparation is high (can obtain 2.1～4.2 mg mL in ultrasonic 2～5 hours
-1Graphene dispersing solution), single-layer graphene proportion large (being higher than 50%), and gained graphene dispersing solution quite stable.
Describe the present invention below in conjunction with specific embodiment.Protection scope of the present invention is not limited with embodiment, but is limited by claim.
Description of drawings
The transmission electron microscope picture of the Graphene of Fig. 1 embodiments of the invention 1 preparation.
The atomic force microscope figure of the Graphene of Fig. 2 embodiments of the invention 1 preparation.
Infrared and the Raman spectrogram of the Graphene of Fig. 3 embodiments of the invention 1 preparation.
Specific embodiments
Embodiment 1
Adding mass ratio in the solvent dimethyl sulfoxide (DMSO) is Trisodium Citrate and the particle diameter≤30 μ m graphite of 2:1, and the starting point concentration of graphite is 30 mg mL
-1, after at room temperature ultrasonic 2～5 hours, centrifugal (3000 rpm, 40 min) remove the unstripped graphite particle of opening, and collection suspension namely gets high density and (can reach 4.2 mg mL
-1) the dispersion liquid of zero defect Graphene.
Transmission electron microscope and atomic force microscope show that graphite is highly peeled away, and the gained lamellar spacing is about 1～3 nm, illustrates that the gained lamella is single or multiple lift (less than 5 layers) Graphene; The intimate disappearance of oxy radical absorption peak and D band shows that these Graphenes form purely the non-structure defective in the FT-IR ﹠ FT-RAMAN spectra.
Embodiment 2
Adding mass ratio in the solvent dimethyl sulfoxide (DMSO) is disodium ethylene diamine tetraacetate and the particle diameter≤30 μ m graphite of 2:1, and the starting point concentration of graphite is 20 mg mL
-1, after at room temperature ultrasonic 2～5 hours, centrifugal (3000 rpm, 40 min) remove the unstripped graphite particle of opening, and collection suspension namely gets high density and (can reach 1.9 mg mL
-1) the dispersion liquid of zero defect Graphene.
Embodiment 3
Adding mass ratio in the solvent dimethyl sulfoxide (DMSO) is sodium tartrate and the particle diameter≤30 μ m graphite of 2:1, and the starting point concentration of graphite is 20 mg mL
-1, after at room temperature ultrasonic 2～5 hours, centrifugal (3000 rpm, 40 min) remove the unstripped graphite particle of opening, and collection suspension namely gets high density and (can reach 1.7 mg mL
-1) the dispersion liquid of zero defect Graphene.
Embodiment 4
Adding mass ratio in the solvent dimethyl sulfoxide (DMSO) is Seignette salt and the particle diameter≤30 μ m graphite of 2:1, and the starting point concentration of graphite is 30 mg mL
-1, after at room temperature ultrasonic 2～5 hours, centrifugal (3000 rpm, 40 min) remove the unstripped graphite particle of opening, and collection suspension namely gets high density and (can reach 2.6 mg mL
-1) the dispersion liquid of zero defect Graphene.
Embodiment 5
Adding mass ratio in the solvent DMF is Trisodium Citrate and the particle diameter≤30 μ m graphite of 2:1, and the starting point concentration of graphite is 20 mg mL
-1, after at room temperature ultrasonic 2～5 hours, centrifugal (3000 rpm, 40 min) remove the unstripped graphite particle of opening, and collection suspension namely gets high density and (can reach 0.57 mg mL
-1) the dispersion liquid of zero defect Graphene.
Embodiment 6
Adding mass ratio in the solvent DMF is disodium ethylene diamine tetraacetate and the particle diameter≤30 μ m graphite of 2:1, and the starting point concentration of graphite is 10 mg mL
-1, after at room temperature ultrasonic 2～5 hours, centrifugal (3000 rpm, 40 min) remove the unstripped graphite particle of opening, and collection suspension namely gets high density and (can reach 0.40 mg mL
-1) the dispersion liquid of zero defect Graphene.
Embodiment 7
Adding mass ratio in the solvent DMF is sodium tartrate and the particle diameter≤30 μ m graphite of 2:1, and the starting point concentration of graphite is 10 mg mL
-1, after at room temperature ultrasonic 2～5 hours, centrifugal (3000 rpm, 40 min) remove the unstripped graphite particle of opening, and collection suspension namely gets high density and (can reach 0.28 mg mL
-1) the dispersion liquid of zero defect Graphene.
Embodiment 8
Adding mass ratio in the solvent DMF is Seignette salt and the particle diameter≤30 μ m graphite of 2:1, and the starting point concentration of graphite is 30 mg mL
-1, after at room temperature ultrasonic 2～5 hours, centrifugal (3000 rpm, 40 min) remove the unstripped graphite particle of opening, and collection suspension namely gets high density and (can reach 1.14 mg mL
-1) the dispersion liquid of zero defect Graphene.
Embodiment 9
Adding mass ratio in the solvent N-Methyl pyrrolidone is Trisodium Citrate and the particle diameter≤30 μ m graphite of 2:1, and the starting point concentration of graphite is 30 mg mL
-1, after at room temperature ultrasonic 2～5 hours, centrifugal (3000 rpm, 40 min) remove the unstripped graphite particle of opening, and collection suspension namely gets high density and (can reach 1.4 mg mL
-1) the dispersion liquid of zero defect Graphene.
Embodiment 10
Adding mass ratio in the solvent N-Methyl pyrrolidone is disodium ethylene diamine tetraacetate and the particle diameter≤30 μ m graphite of 2:1, and the starting point concentration of graphite is 10 mg mL
-1, after at room temperature ultrasonic 2～5 hours, centrifugal (3000 rpm, 40 min) remove the unstripped graphite particle of opening, and collection suspension namely gets high density and (can reach 0.41 mg mL
-1) the dispersion liquid of zero defect Graphene.
Embodiment 11
Adding mass ratio in the solvent N-Methyl pyrrolidone is sodium tartrate and the particle diameter≤30 μ m graphite of 2:1, and the starting point concentration of graphite is 10 mg mL
-1, after at room temperature ultrasonic 2～5 hours, centrifugal (3000 rpm, 40 min) remove the unstripped graphite particle of opening, and collection suspension namely gets high density and (can reach 0.57 mg mL
-1) the dispersion liquid of zero defect Graphene.
Embodiment 12
Adding mass ratio in the solvent N-Methyl pyrrolidone is Seignette salt and the particle diameter≤30 μ m graphite of 2:1, and the starting point concentration of graphite is 20 mg mL
-1, after at room temperature ultrasonic 2～5 hours, centrifugal (3000 rpm, 40 min) remove the unstripped graphite particle of opening, and collection suspension namely gets high density and (can reach 1.12 mg mL
-1) the dispersion liquid of zero defect Graphene.
Claims (7)
1. the preparation method of a zero defect Graphene is characterized in that, will mix in Graphite Powder 99 and the organic salt adding solvent, and mixture carries out supersound process; Mixture after ultrasonic the peeling off is centrifugal, remove unstripped graphite granule, collect suspension, namely obtain the dispersion liquid of zero defect Graphene.
2. the preparation method of Graphene according to claim 1 is characterized in that, described Graphite Powder 99 is chemical pure natural graphite powder, particle diameter≤30 μ m.
3. the preparation method of Graphene according to claim 1 is characterized in that, described organic salt is one or more in disodium ethylene diamine tetraacetate, sodium tartrate, Seignette salt, soluble tartrate, Trisodium Citrate or the Tripotassium Citrate.
4. the preparation method of Graphene according to claim 1 is characterized in that, described solvent is dimethyl sulfoxide (DMSO), DMF or N-Methyl pyrrolidone.
5. the preparation method of Graphene according to claim 1 is characterized in that, the starting point concentration of described graphite is 2～30 mg mL
-1, the starting point concentration of organic salt is 4～60 mg mL
-1
6. the preparation method of Graphene according to claim 1 is characterized in that, in the described method, the ultrasonic temperature of peeling off is room temperature, and the time is 2～5 hours.
7. the preparation method of Graphene according to claim 1 is characterized in that, in the described method, centrifugal rotational speed is 3000 rpm, and centrifugation time is 40 min.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103496691A (en) * | 2013-09-13 | 2014-01-08 | 山东聊城鲁西化工集团有限责任公司 | Preparation method of graphene dispersion liquid |
| CN103839608A (en) * | 2014-01-06 | 2014-06-04 | 沈阳化工大学 | Method for manufacturing conductive graphene film through ink-jet printing |
| CN104108709A (en) * | 2014-07-25 | 2014-10-22 | 深圳新宙邦科技股份有限公司 | Porous graphene and preparation method thereof |
| CN104787758A (en) * | 2015-04-20 | 2015-07-22 | 德阳烯碳科技有限公司 | Method for preparing graphene on large scale |
| CN104787759A (en) * | 2015-04-20 | 2015-07-22 | 德阳烯碳科技有限公司 | Impurity removal method in preparation process of graphene |
| CN108893755A (en) * | 2018-07-09 | 2018-11-27 | 南京师范大学 | Mixing removing one-step method prepares the method and its application of nano-scale molybdenum disulfide and graphene complex |
| CN109036868A (en) * | 2018-09-07 | 2018-12-18 | 南京师范大学 | Graphene oxide assists liquid phase removing preparing graphite alkene/graphene oxide composite material method and its composite material and application |
| CN109133062A (en) * | 2018-10-10 | 2019-01-04 | 西南交通大学 | A kind of overstable Ti3C2The preparation method of suspension |
| CN109665563A (en) * | 2019-01-31 | 2019-04-23 | 内蒙古大学 | A method of it removing natural molybdenite and prepares two-dimentional molybdenum disulfide nano material |
| CN111137866A (en) * | 2020-01-10 | 2020-05-12 | 中国南方电网有限责任公司电网技术研究中心 | Method for preparing boron nitride nanosheet by efficiently stripping h-BN |
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Cited By (17)
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| CN103496691A (en) * | 2013-09-13 | 2014-01-08 | 山东聊城鲁西化工集团有限责任公司 | Preparation method of graphene dispersion liquid |
| CN103496691B (en) * | 2013-09-13 | 2015-09-30 | 鲁西集团有限公司 | A kind of preparation method of graphene dispersing solution |
| CN103839608A (en) * | 2014-01-06 | 2014-06-04 | 沈阳化工大学 | Method for manufacturing conductive graphene film through ink-jet printing |
| CN104108709A (en) * | 2014-07-25 | 2014-10-22 | 深圳新宙邦科技股份有限公司 | Porous graphene and preparation method thereof |
| CN104787758A (en) * | 2015-04-20 | 2015-07-22 | 德阳烯碳科技有限公司 | Method for preparing graphene on large scale |
| CN104787759A (en) * | 2015-04-20 | 2015-07-22 | 德阳烯碳科技有限公司 | Impurity removal method in preparation process of graphene |
| CN104787758B (en) * | 2015-04-20 | 2017-05-03 | 德阳烯碳科技有限公司 | Method for preparing graphene on large scale |
| CN104787759B (en) * | 2015-04-20 | 2017-09-15 | 德阳烯碳科技有限公司 | A kind of impurity-removing method in graphene preparation process |
| CN108893755A (en) * | 2018-07-09 | 2018-11-27 | 南京师范大学 | Mixing removing one-step method prepares the method and its application of nano-scale molybdenum disulfide and graphene complex |
| CN109036868A (en) * | 2018-09-07 | 2018-12-18 | 南京师范大学 | Graphene oxide assists liquid phase removing preparing graphite alkene/graphene oxide composite material method and its composite material and application |
| CN109133062A (en) * | 2018-10-10 | 2019-01-04 | 西南交通大学 | A kind of overstable Ti3C2The preparation method of suspension |
| CN109133062B (en) * | 2018-10-10 | 2021-10-01 | 西南交通大学 | Ultra-stable Ti3C2Method for producing a suspension |
| CN109665563A (en) * | 2019-01-31 | 2019-04-23 | 内蒙古大学 | A method of it removing natural molybdenite and prepares two-dimentional molybdenum disulfide nano material |
| CN111137880A (en) * | 2019-12-18 | 2020-05-12 | 武汉科技大学 | Separation and purification method of graphene |
| CN111137866A (en) * | 2020-01-10 | 2020-05-12 | 中国南方电网有限责任公司电网技术研究中心 | Method for preparing boron nitride nanosheet by efficiently stripping h-BN |
| CN113735098A (en) * | 2020-05-29 | 2021-12-03 | 中国石油天然气股份有限公司 | Nitrogen-doped carbon nanoring, and preparation method and application thereof |
| CN113735098B (en) * | 2020-05-29 | 2023-08-22 | 中国石油天然气股份有限公司 | Nitrogen-doped carbon nano ring, and preparation method and application thereof |
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Application publication date: 20130206 |