CN104944421A - High-conductivity graphene preparing method - Google Patents
High-conductivity graphene preparing method Download PDFInfo
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- CN104944421A CN104944421A CN201510400084.2A CN201510400084A CN104944421A CN 104944421 A CN104944421 A CN 104944421A CN 201510400084 A CN201510400084 A CN 201510400084A CN 104944421 A CN104944421 A CN 104944421A
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- graphene
- expanded graphite
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Abstract
The invention relates to a graphene preparing method, in particular to a high-conductivity graphene preparing method. The method is used for solving the problems that according to an existing preparing method, low-cost batched production can be difficultly achieved on the graphene with the stable performance and high conductivity, many steps exist, and factors influencing the product stability in the preparing process are multiple and complex. According to the scheme, the method includes the steps that firstly, expansible graphite is heated, and the expanded graphite is prepared; secondly, the expanded graphite is stripped off under the double action of organic matter with low surface tension and ultrasounds, impurities are removed through secondary centrifugation, secondary centrifugation sediment is dried, and high-conductivity graphene is obtained. The high-conductivity graphene preparing method has the advantages that the expanded graphite is stripped off under the double action of the organic solvent with the low surface tension and the ultrasounds, a redox reaction does not exist, impurities are not introduced, and compared with a traditional chemical preparing method, the generated graphene is few in defect, few in layer and higher in conductivity; a special device is not needed, the preparing method is simple and convenient, the stability of the performance of the prepared graphene is good, the performance is good, and industrial production is facilitated.
Description
Technical field
The present invention relates to graphene preparation method, be specially high-electroconductivity graphene preparation method.
Background technology
In Graphene, the carbon atom of carbon atom and surrounding forms stable benzene six-membered ring structure, constitutes its elementary cell.Graphene is the thinnest in the world is also the hardest nano material, and it is almost completely transparent, only absorbs the light of 2.3%; Thermal conductivity is up to 5300 W/(mK), higher than carbon nanotube and diamond, under normal temperature, its electronic mobility is more than 15000 cm
2/ (Vs), again than CNT (carbon nano-tube) or silicon wafer height, and resistivity only about 10
-6Ω cm, than copper or silver lower, be the material that world resistivity is minimum.Because its resistivity is extremely low, the speed that electronics runs is exceedingly fast, and is therefore expected to be widely used as electro-conductive material.The main method preparing Graphene at present has the multiple preparation methods such as mechanical stripping method, epitaxial growth method, oxidation reduction process and chemical vapor infiltration (CVD).Mechanically peel method, epitaxial growth method and chemical vapor infiltration prepare the shortcomings such as the efficiency of Graphene is lower, condition is harsh, apparatus expensive, are difficult to low cost batch and prepare Graphene material.And the redox chemical preparation process of most popular Hummer's is relatively simple because of preparation technology so far, and do not need special expensive equipment, what be considered to have most at present application prospect prepares Graphene method, but, the structure of the Graphene synthesized by chemistry redox method is destroyed and is had remarkable defect, electric conductivity significantly reduces, and is unfavorable for the application as high conductive material; Chemistry redox method preparation process is more in addition, and graphite oxide preparation process influence factor is many and complicated, greatly have impact on the preparation stability of graphene product, is unfavorable for industrialization.Therefore, a kind of can low cost batch production, preparation method is simple, product stability good, electric conductivity is high graphene preparation method being extremely necessary is studied.
Summary of the invention
The present invention solves existing graphene preparation method and is difficult to low cost and produces the Graphene that performance is stablized, electric conductivity is high in batches, and existing preparation method's step is many, affect the many and problem of complexity of the factor of product stability in preparation process, provides a kind of high-electroconductivity graphene preparation method.
The present invention is achieved by the following technical solutions:
High-electroconductivity graphene preparation method, is achieved through the following technical solutions:
1), expansible black lead material is placed in process furnace heats, obtain expanded graphite;
2), a certain amount of expanded graphite being dispersed in surface tension is less than in the liguid organic solvent of 30dyn/cm, under-5 DEG C ~ 100 DEG C conditions, supersound process 1.5 ~ 3.5h, then with 500 ~ 1000 revs/min of centrifugal disgorging, then obtain secondary precipitate so that the rotating speed being greater than 1000 revs/min is centrifugal further, obtain high-electroconductivity graphene by after secondary precipitate drying, the mass ratio of described expanded graphite and organic solvent is 1:100 ~ 300.
Surface of organic solvent tension force is less than 30dyn/cm, is beneficial to expanded graphite and disperses in organic solvent, makes expanded graphite be conducive to peeling off.First time the centrifugal Graphene impurity for filtering multilayered structure, what obtain with higher rotating speed secondary centrifuging is the Graphene of single layer structure, for the present invention is to be prepared.
Expansible black lead in described step 1) is the expansible black lead that inflatable degree is greater than 50ml/g.The inflatable degree of expansible black lead is greater than 50ml/g, can ensure the single layer structure of final product.Expanded graphite in described step 1) is that expansible black lead is heated to 600 ~ 800 DEG C and keeps 30s ~ 1min process obtained in process furnace.Heating temperature 600 ~ 800 DEG C also keeps 30s ~ 1min, ensures that expansible black lead is fully expanded.Described step 2) in be also added with the fluorine-containing organic surfactant reagent of organic solvent quality 1wt% in liguid organic solvent.Fluorine-containing organic surfactant reagent can reduce the surface tension of organic solvent, is more beneficial to the stripping of expanded graphite and is uniformly dispersed in organic solvent.The liguid organic solvent that described surface tension is less than 30dyn/cm comprises acetone, tetrahydrofuran (THF), ethanol, dimethyl formamide, alkanes fluid organic material matter.Described step 2) in fluorine-containing organic surfactant reagent, including, but not limited to perfluor 2-butyl tetrahydrofuran, perfluor triethylamine.The power of described supersound process is greater than 120W.
The present invention compared with prior art has the following advantages: 1, under the organic solvent and ultrasonic dual function of low surface tension, peel off expanded graphite, not oxidation reduction reaction, do not introduce impurity, compared with traditional chemical preparation method, the Graphene defect generated is few, the number of plies is few (individual layer), and electric conductivity is higher (can reach 220 Scm
-1); 2, without the need to specific installation, preparation method is easy, good stability, excellent performance, is beneficial to industrialization and produces.
Accompanying drawing explanation
Fig. 1 is graphene organic dispersion optical photograph in kind prepared by the present invention; Graphene solution good stability in organic phase prepared by the present invention is described;
Fig. 2 is the Raman spectrum of graphene product prepared by the present invention; As seen from the figure, the Graphene defect prepared of the present invention is less;
Fig. 3 is graphene product AMF figure prepared by the present invention; As seen from the figure, Graphene thickness prepared by the present invention is only about 1.0nm, is single-layer graphene.
Embodiment
Embodiment one: high-electroconductivity graphene preparation method, comprises following operation steps:
1) be, by inflatable degree that the expansible black lead of 51ml/g is placed in process furnace and is heated to 650 DEG C and keeps 1min, obtain expanded graphite;
2), by a certain amount of expanded graphite, the surface tension be dispersed in containing perfluor 2-butyl tetrahydrofuran is less than in the acetone of 30dyn/cm, the mass ratio of described expanded graphite and organic solvent is 1:200, described surface-active agents content is 0.01wt%, under 25 DEG C of conditions, with the power ultrasonic process 2.5h of 121W, then with 890 revs/min of centrifugal disgorging, then obtain secondary precipitate so that the rotating speed of 1100 revs/min is centrifugal further, obtain high-electroconductivity graphene by after secondary precipitate drying.
Embodiment two: high-electroconductivity graphene preparation method, comprises following operation steps:
1) be, by inflatable degree that the expansible black lead of 60ml/g is placed in process furnace and is heated to 800 DEG C and keeps 30s, obtain expanded graphite;
2), a certain amount of expanded graphite surface tension be dispersed in containing perfluor triethylamine is less than in the tetrahydrofuran (THF) of 30dyn/cm, the mass ratio of described expanded graphite and organic solvent is 1:250, described surface-active agents content is 0.75wt%, under 70 DEG C of conditions, with the power ultrasonic process 1.5h of 150W, then with 650 revs/min of centrifugal disgorging, then obtain secondary precipitate so that the rotating speed of 2000 revs/min is centrifugal further, obtain high-electroconductivity graphene by after secondary precipitate drying.
Embodiment three: high-electroconductivity graphene preparation method, comprises following operation steps:
1) be, by inflatable degree that the expansible black lead of 80ml/g is placed in process furnace and is heated to 700 DEG C and keeps 45s, obtain expanded graphite;
2), by a certain amount of expanded graphite, the surface tension be dispersed in containing perfluor 2-butyl tetrahydrofuran is less than in the ethanol of 30dyn/cm, the mass ratio of described expanded graphite and organic solvent is 1:100, described surface-active agents content is 1wt%, under 100 DEG C of conditions, with the power ultrasonic process 2h of 200W, then with 1000 revs/min of centrifugal disgorging, then obtain secondary precipitate so that the rotating speed of 3000 revs/min is centrifugal further, obtain high-electroconductivity graphene by after secondary precipitate drying.
Embodiment four: high-electroconductivity graphene preparation method, comprises following operation steps:
1) be, by inflatable degree that the expansible black lead of 60ml/g is placed in process furnace and is heated to 600 DEG C and keeps 50s, obtain expanded graphite;
2), a certain amount of expanded graphite surface tension be dispersed in containing perfluor triethylamine is less than in the dimethyl formamide of 30dyn/cm, the mass ratio of described expanded graphite and organic solvent is 1:150, described surface-active agents content is 0.5wt%, under 50 DEG C of conditions, with the power ultrasonic process 3.5h of 160W, then with 500 revs/min of centrifugal disgorging, then obtain secondary precipitate so that the rotating speed of 1500 revs/min is centrifugal further, obtain high-electroconductivity graphene by after secondary precipitate drying.
Embodiment five: high-electroconductivity graphene preparation method, comprises following operation steps:
1) be, by inflatable degree that the expansible black lead of 70ml/g is placed in process furnace and is heated to 750 DEG C and keeps 40s, obtain expanded graphite;
2), by a certain amount of expanded graphite, the surface tension be dispersed in containing perfluor 2-butyl tetrahydrofuran is less than in the alkanes fluid organic material matter of 30dyn/cm, the mass ratio of described expanded graphite and organic solvent is 1:300, described surface-active agents content is 0.25wt%, under-5 DEG C of conditions, with the power ultrasonic process 3h of 130W, then with 750 revs/min of centrifugal disgorging, then obtain secondary precipitate so that the rotating speed of 5000 revs/min is centrifugal further, obtain high-electroconductivity graphene by after secondary precipitate drying.
Claims (10)
1. a high-electroconductivity graphene preparation method, is characterized in that: be achieved through the following technical solutions:
1), expansible black lead material is placed in process furnace heats, obtain expanded graphite;
2), a certain amount of expanded graphite being dispersed in surface tension is less than in the liguid organic solvent of 30dyn/cm, under-5 DEG C ~ 100 DEG C conditions, supersound process 1.5 ~ 3.5h, then with 500 ~ 1000 revs/min of centrifugal disgorging, then obtain secondary precipitate so that the rotating speed being greater than 1000 revs/min is centrifugal further, obtain high-electroconductivity graphene by after secondary precipitate drying, the mass ratio of described expanded graphite and organic solvent is 1:100 ~ 300.
2. high-electroconductivity graphene preparation method according to claim 1, is characterized in that: the expansible black lead in described step 1) is the expansible black lead that inflatable degree is greater than 50ml/g.
3. high-electroconductivity graphene preparation method according to claim 2, is characterized in that: the expanded graphite in described step 1) is that expansible black lead is heated to 600 ~ 800 DEG C and keeps 30s ~ 1min process obtained in process furnace.
4. the high-electroconductivity graphene preparation method according to claim 1 or 2 or 3, is characterized in that: described step 2) in be also added with the fluorine-containing organic surfactant reagent of organic solvent quality 1wt% in liguid organic solvent.
5. the high-electroconductivity graphene preparation method according to claim 1 or 2 or 3, is characterized in that: the fluid organic material that described surface tension is less than 30dyn/cm comprises acetone, tetrahydrofuran (THF), ethanol, dimethyl formamide, alkanes fluid organic material matter.
6. high-electroconductivity graphene preparation method according to claim 4, is characterized in that: the fluid organic material that described surface tension is less than 30dyn/cm comprises acetone, tetrahydrofuran (THF), ethanol, dimethyl formamide, alkanes fluid organic material matter.
7. high-electroconductivity graphene preparation method according to claim 5, is characterized in that: described step 2) in fluorine-containing organic surface active agent, including, but not limited to perfluor 2-butyl tetrahydrofuran, perfluor triethylamine.
8. high-electroconductivity graphene preparation method according to claim 6, is characterized in that: described step 2) in fluorine-containing organic surface active agent, including, but not limited to perfluor 2-butyl tetrahydrofuran, perfluor triethylamine.
9. high-electroconductivity graphene preparation method according to claim 7, is characterized in that: the power of described supersound process is greater than 120W.
10. high-electroconductivity graphene preparation method according to claim 8, is characterized in that: the power of described supersound process is greater than 120W.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108569687A (en) * | 2017-03-07 | 2018-09-25 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of graphene three-dimensional porous material |
| CN109705407A (en) * | 2018-12-17 | 2019-05-03 | 苏州鼎烯聚材纳米科技有限公司 | A kind of production method of graphene rubber concentrate feed and graphene rubber |
| CN109728300A (en) * | 2018-12-27 | 2019-05-07 | 宁波杉元石墨烯科技有限公司 | A kind of lithium battery electrocondution slurry and preparation method thereof containing different defect graphenes |
-
2015
- 2015-07-10 CN CN201510400084.2A patent/CN104944421A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108569687A (en) * | 2017-03-07 | 2018-09-25 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of graphene three-dimensional porous material |
| CN109705407A (en) * | 2018-12-17 | 2019-05-03 | 苏州鼎烯聚材纳米科技有限公司 | A kind of production method of graphene rubber concentrate feed and graphene rubber |
| CN109705407B (en) * | 2018-12-17 | 2021-06-08 | 苏州鼎烯聚材纳米科技有限公司 | Graphene rubber concentrated material and production method of graphene rubber |
| CN109728300A (en) * | 2018-12-27 | 2019-05-07 | 宁波杉元石墨烯科技有限公司 | A kind of lithium battery electrocondution slurry and preparation method thereof containing different defect graphenes |
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Application publication date: 20150930 |