CN103964429B - A kind of preparation method of Graphene - Google Patents
A kind of preparation method of Graphene Download PDFInfo
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- CN103964429B CN103964429B CN201410225832.3A CN201410225832A CN103964429B CN 103964429 B CN103964429 B CN 103964429B CN 201410225832 A CN201410225832 A CN 201410225832A CN 103964429 B CN103964429 B CN 103964429B
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Abstract
The invention discloses a kind of preparation method of Graphene, is obtained by following steps: 1) be added in hydrogen peroxide solution by graphite, stir 30min ~ 5h; 2) by 1) products therefrom under vacuum tightness 100Pa ~ 1000Pa, be warming up to 100 ~ 400 DEG C, maintain constant temperature 5h ~ 12h; 3) by 2) product ultrasonic vibration 30min ~ 1h; 4) by 3) product is added in hydrogen peroxide solution, stirs 2h ~ 8h; 5) by 4) obtain Graphene after the dry 12h ~ 24h of product vacuum.The beneficial effect of the preparation method of Graphene provided by the invention: decomposing hydrogen dioxide solution generates oxygen G&W, and make in process and there is not dissolvent residual, the Graphene performance of generation is more stable, and electric property is good.
Description
Technical field
The present invention relates to technical field of graphene, particularly a kind of preparation method of Graphene.
Background technology
Graphene (Graphene) is by the bi-dimensional cellular shape structure of the tightly packed one-tenth of carbon atom, can be counted as " graphite flake " that one deck is stripped, be considered to the parent of the body phase graphite of the soccerballene of zero dimension, the carbon nanotube of one dimension and three-dimensional, thus form the complete Tan Xi family of soccerballene, carbon nanotube, diamond and graphite.The physical and chemical performance excellent due to Graphene and widely application prospect, the technology preparing Graphene is made to be able to fast development, at present, the preparation of Graphene mainly contains two kinds of approach, be the method from top to bottom adopting various physical chemistry means to peel off graphite, another kind is by the method for small molecules synthesizing graphite alkene from bottom to top.Wherein, method from top to bottom has mechanical stripping method, graphite oxide reduction method and compound between graphite layers approach; And method from bottom to top has deposition growing method and chemical synthesis.The Graphene defect that in these methods prepared by compound between graphite layers approach is few, quality is high, but because organic solvent and tensio-active agent remain in obtained Graphene, its electric property is affected.
Based on the above, the exploitation of a kind of preparation method of Graphene of improvement is by necessary property.
Summary of the invention
For the problems referred to above, the invention provides a kind of preparation method of Graphene of improvement, by carrying out twice decomposing hydrogen dioxide solution and thermal expansion reaction between graphite flake layer, graphite flake layer spacing being increased to separated from one another, thus obtained Graphene.The preparation method of the Graphene of this improvement can avoid the problems such as organic solvent and tensio-active agent remain.
The preparation method of Graphene disclosed by the invention is obtained by following steps:
A preparation method for Graphene, is characterized in that, is to be obtained by following steps:
1) graphite is added in hydrogen peroxide solution, stirs 30min ~ 5h.Decomposing hydrogen dioxide solution generates oxygen, in graphite flake inter-level diffusion, forms the peeling force between graphite flake layer;
2) by 1) products therefrom under vacuum tightness 100Pa ~ 1000Pa, be warming up to 100 ~ 400 DEG C, maintain constant temperature 5h ~ 12h.Under high-temperature and high-pressure conditions, graphite flake layer spacing strengthens further;
3) by 2) product ultrasonic vibration 30min ~ 1h.Ultrasonic vibration effect makes graphite flake layer by layer apart from strengthening further;
4) by 3) product is added in hydrogen peroxide solution, stirs 2h ~ 8h.Peeled off by secondary hydrogen peroxide intercalation, graphite flake layer is thoroughly separated, generate Graphene;
5) by 4) obtain Graphene after the dry 12h ~ 24h of product vacuum.
Preferably, the preparation method of described Graphene, wherein, step 1) temperature of reaction is 50 ~ 115 DEG C.
Preferably, the preparation method of described Graphene, wherein, described hydrogen peroxide solution concentration is 5% ~ 40%.
Preferably, the preparation method of described Graphene, wherein, is added with suds-stabilizing agent in described hydrogen peroxide solution, and described suds-stabilizing agent is polyvinyl alcohol.Suds-stabilizing agent can improve bubble stability, extends the bubble burst transformation period.
Preferably, the preparation method of described Graphene, wherein, described polyvinyl alcohol concentration is 0.01g/mL ~ 0.2g/mL.
Preferably, the preparation method of described Graphene, wherein, step 2) stirring velocity is 200 ~ 500 turns/min.
Preferably, the preparation method of described Graphene, wherein, step 3) ultrasonic vibration carries out at normal temperatures.
Preferably, the preparation method of described Graphene, wherein, step 4) temperature of reaction is 50 ~ 135 DEG C.
Preferably, the preparation method of described Graphene, wherein, step 5) vacuum drying temperature is carry out at 60 DEG C ~ 120 DEG C.
The beneficial effect of the preparation method of Graphene provided by the invention: decomposing hydrogen dioxide solution generates oxygen G&W, and make in process and there is not dissolvent residual, the Graphene performance of generation is more stable, and electric property is good.
Embodiment
The present invention is described in further detail below, can implement according to this with reference to specification sheets word to make those skilled in the art.
Embodiment 1
The present embodiment provides a kind of preparation method of Graphene, is to be obtained by following steps:
1) be added in hydrogen peroxide solution by graphite, temperature of reaction is 50 DEG C, and stir 5h, described hydrogen peroxide solution concentration is 5%.Decomposing hydrogen dioxide solution generates oxygen, in graphite flake inter-level diffusion, forms the peeling force between graphite flake layer.Be added with suds-stabilizing agent in described hydrogen peroxide solution, described suds-stabilizing agent is polyvinyl alcohol, and described polyvinyl alcohol concentration is 0.01g/mL.Suds-stabilizing agent can improve bubble stability, extends the bubble burst transformation period;
2) by 1) products therefrom under vacuum tightness 100Pa, be warming up to 400 DEG C, maintain constant temperature 5h.Under high-temperature and high-pressure conditions, graphite flake layer spacing strengthens further;
3) by 2) ultrasonic vibration 30min under product normal temperature.Ultrasonic vibration effect makes graphite flake layer by layer apart from strengthening further;
4) by 3) product is added in hydrogen peroxide solution, and stir 2h, stirring velocity is 500 turns/min, and temperature of reaction is 135 DEG C.Peeled off by a hydrogen peroxide intercalation again, graphite flake layer is thoroughly separated, generate Graphene;
5) by 4) product at 60 DEG C, obtain Graphene after vacuum-drying 24h.
The lamellar spacing of obtained Graphene is 15nm; The specific surface of described Graphene is 650m
2/ g.Graphene electrodes is through constant current charge-discharge under 0.05A/g current density, and to calculate capacity ratio capacity be 155F/g, efficiency E is 99.2%.
Embodiment 2
The present embodiment provides a kind of preparation method of Graphene, is to be obtained by following steps:
1) be added in hydrogen peroxide solution by graphite, temperature of reaction is 115 DEG C, and stir 30min, described hydrogen peroxide solution concentration is 40%.Decomposing hydrogen dioxide solution generates oxygen, in graphite flake inter-level diffusion, forms the peeling force between graphite flake layer.Be added with suds-stabilizing agent in described hydrogen peroxide solution, described suds-stabilizing agent is polyvinyl alcohol, and described polyvinyl alcohol concentration is 0.2g/mL.Suds-stabilizing agent can improve bubble stability, extends the bubble burst transformation period;
2) by 1) products therefrom under vacuum tightness 1000Pa, be warming up to 100 DEG C, maintain constant temperature 12h.Under high-temperature and high-pressure conditions, graphite flake layer spacing strengthens further;
3) by 2) ultrasonic vibration 1h under product normal temperature.Ultrasonic vibration effect makes graphite flake layer by layer apart from strengthening further;
4) by 3) product is added in hydrogen peroxide solution, and stir 8h, stirring velocity is 200 turns/min, and temperature of reaction is 50 DEG C.Peeled off by a hydrogen peroxide intercalation again, graphite flake layer is thoroughly separated, generate Graphene;
5) by 4) product at 120 DEG C, obtain Graphene after vacuum-drying 12h.
The lamellar spacing of obtained Graphene is 9nm; The specific surface of described Graphene is 1200m
2/ g.Graphene electrodes is through constant current charge-discharge under 0.05A/g current density, and to calculate capacity ratio capacity be 190F/g, efficiency E is 99.5%.
Embodiment 3
The present embodiment provides a kind of preparation method of Graphene, is to be obtained by following steps:
1) be added in hydrogen peroxide solution by graphite, temperature of reaction is 65 DEG C, and stir 1h, described hydrogen peroxide solution concentration is 30%.Decomposing hydrogen dioxide solution generates oxygen, in graphite flake inter-level diffusion, forms the peeling force between graphite flake layer.Be added with suds-stabilizing agent in described hydrogen peroxide solution, described suds-stabilizing agent is polyvinyl alcohol, and described polyvinyl alcohol concentration is 0.05g/mL.Suds-stabilizing agent can improve bubble stability, extends the bubble burst transformation period;
2) by 1) products therefrom under vacuum tightness 500Pa, be warming up to 200 DEG C, maintain constant temperature 6h.Under high-temperature and high-pressure conditions, graphite flake layer spacing strengthens further;
3) by 2) ultrasonic vibration 40min under product normal temperature.Ultrasonic vibration effect makes graphite flake layer by layer apart from strengthening further;
4) by 3) product is added in hydrogen peroxide solution, and stir 4h, stirring velocity is 300 turns/min, and temperature of reaction is 75 DEG C.Peeled off by a hydrogen peroxide intercalation again, graphite flake layer is thoroughly separated, generate Graphene;
5) by 4) product at 70 DEG C, obtain Graphene after vacuum-drying 14h.
The lamellar spacing of obtained Graphene is 3.5nm; The specific surface of described Graphene is 1500m
2/ g.Graphene electrodes is through constant current charge-discharge under 0.05A/g current density, and to calculate capacity ratio capacity be 178F/g, efficiency E is 99.4%.
Embodiment 4
The present embodiment provides a kind of preparation method of Graphene, is to be obtained by following steps:
1) be added in hydrogen peroxide solution by graphite, temperature of reaction is 80 DEG C, and stir 2h, described hydrogen peroxide solution concentration is 25%.Decomposing hydrogen dioxide solution generates oxygen, in graphite flake inter-level diffusion, forms the peeling force between graphite flake layer.Be added with suds-stabilizing agent in described hydrogen peroxide solution, described suds-stabilizing agent is polyvinyl alcohol, and described polyvinyl alcohol concentration is 0.1g/mL.Suds-stabilizing agent can improve bubble stability, extends the bubble burst transformation period;
2) by 1) products therefrom under vacuum tightness 600Pa, be warming up to 300 DEG C, maintain constant temperature 7h.Under high-temperature and high-pressure conditions, graphite flake layer spacing strengthens further;
3) by 2) ultrasonic vibration 40min under product normal temperature.Ultrasonic vibration effect makes graphite flake layer by layer apart from strengthening further;
4) by 3) product is added in hydrogen peroxide solution, and stir 6h, stirring velocity is 300 turns/min, and temperature of reaction is 95 DEG C.Peeled off by a hydrogen peroxide intercalation again, graphite flake layer is thoroughly separated, generate Graphene;
5) by 4) product at 80 DEG C, obtain Graphene after vacuum-drying 20h.
The lamellar spacing of obtained Graphene is 4nm; The specific surface of described Graphene is 1300m
2/ g.Graphene electrodes is through constant current charge-discharge under 0.05A/g current density, and to calculate capacity ratio capacity be 146F/g, efficiency E is 99.3%.
Embodiment 5
The present embodiment provides a kind of preparation method of Graphene, is to be obtained by following steps:
1) be added in hydrogen peroxide solution by graphite, temperature of reaction is 75 DEG C, and stir 4h, described hydrogen peroxide solution concentration is 30%.Decomposing hydrogen dioxide solution generates oxygen, in graphite flake inter-level diffusion, forms the peeling force between graphite flake layer.Be added with suds-stabilizing agent in described hydrogen peroxide solution, described suds-stabilizing agent is polyvinyl alcohol, and described polyvinyl alcohol concentration is 0.02g/mL.Suds-stabilizing agent can improve bubble stability, extends the bubble burst transformation period;
2) by 1) products therefrom under vacuum tightness 300Pa, be warming up to 200 DEG C, maintain constant temperature 7h.Under high-temperature and high-pressure conditions, graphite flake layer spacing strengthens further;
3) by 2) ultrasonic vibration 50min under product normal temperature.Ultrasonic vibration effect makes graphite flake layer by layer apart from strengthening further;
4) by 3) product is added in hydrogen peroxide solution, and stir 4h, stirring velocity is 300 turns/min, and temperature of reaction is 105 DEG C.Peeled off by a hydrogen peroxide intercalation again, graphite flake layer is thoroughly separated, generate Graphene;
5) by 4) product at 90 DEG C, obtain Graphene after vacuum-drying 18h.
The lamellar spacing of obtained Graphene is 3nm; The specific surface of described Graphene is 1050m
2/ g.Graphene electrodes is through constant current charge-discharge under 0.05A/g current density, and to calculate capacity ratio capacity be 158F/g, efficiency E is 99.4%.
Although embodiment of the present invention are open as above, but it is not restricted to listed in specification sheets and embodiment utilization, it can be applied to various applicable the field of the invention completely, for those skilled in the art, can easily realize other amendment, therefore do not deviating under the universal that claim and equivalency range limit, the present invention is not limited to specific details.
Claims (9)
1. a preparation method for Graphene, is characterized in that, is to be obtained by following steps:
1) graphite is added in hydrogen peroxide solution, stirs 30min ~ 5h;
2) by 1) products therefrom under vacuum tightness 100Pa ~ 1000Pa, be warming up to 100 ~ 400 DEG C, maintain constant temperature 5h ~ 12h;
3) by 2) product ultrasonic vibration 30min ~ 1h;
4) by 3) product is added in hydrogen peroxide solution, stirs 2h ~ 8h;
5) by 4) obtain Graphene after the dry 12h ~ 24h of product vacuum.
2. the preparation method of Graphene according to claim 1, is characterized in that, step 1) temperature of reaction is 50 ~ 115 DEG C.
3. the preparation method of Graphene according to claim 1, is characterized in that, described hydrogen peroxide solution concentration is 5% ~ 40%.
4. the preparation method of Graphene according to claim 3, is characterized in that, is added with suds-stabilizing agent in described hydrogen peroxide solution, and described suds-stabilizing agent is polyvinyl alcohol.
5. the preparation method of Graphene according to claim 4, is characterized in that, described polyvinyl alcohol concentration is 0.01g/mL ~ 0.2g/mL.
6. the preparation method of Graphene according to claim 1, is characterized in that, step 2) stirring velocity is 200 ~ 500 turns/min.
7. the preparation method of Graphene according to claim 1, is characterized in that, step 3) ultrasonic vibration carries out at normal temperatures.
8. the preparation method of Graphene according to claim 1, is characterized in that, step 4) temperature of reaction is 50 ~ 135 DEG C.
9. the preparation method of Graphene according to claim 1, is characterized in that, step 5) vacuum drying temperature is carry out at 60 DEG C ~ 120 DEG C.
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| CN106206050A (en) * | 2016-06-29 | 2016-12-07 | 南京邮电大学 | A kind of laser reduction prepares the method for porous graphene |
| CN110697796B (en) * | 2019-10-09 | 2022-04-08 | 福建江夏学院 | Green and efficient synthesis method of transition metal oxyhydroxide ultrathin nanosheets |
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| CN101591014A (en) * | 2009-06-30 | 2009-12-02 | 湖北大学 | A kind of method of realizing large-scale preparation of monolayer oxidized graphene |
| CN103539108A (en) * | 2013-10-22 | 2014-01-29 | 泰山医学院 | Method for preparing graphene oxide |
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| CN101591014A (en) * | 2009-06-30 | 2009-12-02 | 湖北大学 | A kind of method of realizing large-scale preparation of monolayer oxidized graphene |
| CN103539108A (en) * | 2013-10-22 | 2014-01-29 | 泰山医学院 | Method for preparing graphene oxide |
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| Synthesis of few-layered graphene by H2O2 plasma etching of graphite;Guixia Zhao et al;《APPLIED PHYSICS LETTERS》;20110506;第98卷;183114-1页左栏第2段，图1-4 * |
| Sythesis and Characterization of Exfoliated Graphite(EG) and to Use it as a Reinforcement in Zn-based Metal Matrix Composites;Syed Nasimul Alam et al;《2013 MRS FALL MEETING & EXHIBIT》;20131231;Experimental，TEM of Exfoliated Graphite，Raman Spectroscopy * |
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