CN103964429A - Preparation method of graphene - Google Patents
Preparation method of graphene Download PDFInfo
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- CN103964429A CN103964429A CN201410225832.3A CN201410225832A CN103964429A CN 103964429 A CN103964429 A CN 103964429A CN 201410225832 A CN201410225832 A CN 201410225832A CN 103964429 A CN103964429 A CN 103964429A
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Abstract
The invention discloses a preparation method of graphene, which comprises the following steps: 1) adding graphite into an oxydol solution, and stirring for 30 minutes-5 hours; 2) heating the product obtained in the step 1) to 100-400 DEG C under the vacuum degree of 100-1000Pa, and keeping the temperature constant for 5-12 hours; 3) carrying out ultrasonic oscillation on the product in the step 2) for 30 minutes-1 hour; 4) adding the product in the step 3) into an oxydol solution, and stirring for 2-8 hours; and 5) carrying out vacuum drying on the product in the step 4) for 12-24 hours to obtain the graphene. The oxydol is decomposed into oxygen and water, so no solvent residue is left in the preparation process; and the generated graphene has the advantages of stable performance and favorable electric properties.
Description
Technical field
The present invention relates to Graphene technical field, particularly a kind of preparation method of Graphene.
Background technology
Graphene (Graphene) is the bi-dimensional cellular shape structure by the tightly packed one-tenth of carbon atom, can be counted as " graphite flake " that one deck is stripped from, be considered to the parent of soccerballene, the carbon nanotube of one dimension and the body phase graphite of three-dimensional of zero dimension, formed thus the complete Tan Xi family of soccerballene, carbon nanotube, diamond and graphite.Due to the good physical and chemical performance of Graphene and application prospect widely, make the technology of preparing Graphene be able to fast development, at present, the preparation of Graphene mainly contains two kinds of approach, be to adopt various physical chemistry means to peel off a method from top to bottom for graphite, another kind is by the small molecules method of 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.Graphene defect that in these methods prepared by compound between graphite layers approach is few, quality is high, but in the Graphene making because of organic solvent and tensio-active agent residual, its electric property is affected.
Based on the above, a kind of preparation method's of improved Graphene exploitation is by necessary property.
Summary of the invention
For the problems referred to above, the invention provides a kind of preparation method of improved Graphene, by carry out twice decomposing hydrogen dioxide solution and thermal expansion reaction between graphite flake layer, graphite flake layer spacing is increased to separated from one another, thereby make Graphene.The preparation method of this improved Graphene can avoid organic solvent and the problem such as tensio-active agent is residual.
The preparation method of Graphene disclosed by the invention is to make by following steps:
A preparation method for Graphene, is characterized in that, is to make 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 further strengthens;
3) by 2) the ultrasonic concussion of product 30min～1h.Ultrasonic concussion effect makes graphite flake layer by layer apart from further strengthening;
4) by 3) product is added in hydrogen peroxide solution, stirs 2h～8h.Peel off by secondary hydrogen peroxide intercalation, graphite flake layer is thoroughly separated, generate Graphene;
5) by 4) obtain Graphene after product vacuum-drying 12h～24h.
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 turn/min.
Preferably, the preparation method of described Graphene, wherein, step 3) ultrasonic concussion 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 to carry out at 60 DEG C～120 DEG C.
The preparation method's of Graphene provided by the invention beneficial effect: decomposing hydrogen dioxide solution generates oxygen G&W, makes in process and does not have dissolvent residual, and the Graphene performance of generation is more stable, and electric property is good.
Embodiment
The present invention is described in further detail below, to make those skilled in the art can implement according to this with reference to specification sheets word.
Embodiment 1
The present embodiment provides a kind of preparation method of Graphene, is to make by following steps:
1) graphite is added in hydrogen peroxide solution, temperature of reaction is 50 DEG C, stirs 5h, and 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.In described hydrogen peroxide solution, be added with suds-stabilizing agent, 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 further strengthens;
3) by 2) ultrasonic concussion 30min under product normal temperature.Ultrasonic concussion effect makes graphite flake layer by layer apart from further strengthening;
4) by 3) product is added in hydrogen peroxide solution, stirs 2h, and stirring velocity is 500 turn/min, and temperature of reaction is 135 DEG C.Peel off by a hydrogen peroxide intercalation again, graphite flake layer is thoroughly separated, generate Graphene;
5) by 4) product at 60 DEG C, after vacuum-drying 24h, obtain Graphene.
The lamellar spacing of the Graphene making 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 calculating capacity ratio capacity is 155F/g, and efficiency E is 99.2%.
Embodiment 2
The present embodiment provides a kind of preparation method of Graphene, is to make by following steps:
1) graphite is added in hydrogen peroxide solution, temperature of reaction is 115 DEG C, stirs 30min, and 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.In described hydrogen peroxide solution, be added with suds-stabilizing agent, 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 further strengthens;
3) by 2) ultrasonic concussion 1h under product normal temperature.Ultrasonic concussion effect makes graphite flake layer by layer apart from further strengthening;
4) by 3) product is added in hydrogen peroxide solution, stirs 8h, and stirring velocity is 200 turn/min, and temperature of reaction is 50 DEG C.Peel off by a hydrogen peroxide intercalation again, graphite flake layer is thoroughly separated, generate Graphene;
5) by 4) product at 120 DEG C, after vacuum-drying 12h, obtain Graphene.
The lamellar spacing of the Graphene making 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 calculating capacity ratio capacity is 190F/g, and efficiency E is 99.5%.
Embodiment 3
The present embodiment provides a kind of preparation method of Graphene, is to make by following steps:
1) graphite is added in hydrogen peroxide solution, temperature of reaction is 65 DEG C, stirs 1h, and 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.In described hydrogen peroxide solution, be added with suds-stabilizing agent, 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 further strengthens;
3) by 2) ultrasonic concussion 40min under product normal temperature.Ultrasonic concussion effect makes graphite flake layer by layer apart from further strengthening;
4) by 3) product is added in hydrogen peroxide solution, stirs 4h, and stirring velocity is 300 turn/min, and temperature of reaction is 75 DEG C.Peel off by a hydrogen peroxide intercalation again, graphite flake layer is thoroughly separated, generate Graphene;
5) by 4) product at 70 DEG C, after vacuum-drying 14h, obtain Graphene.
The lamellar spacing of the Graphene making 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 calculating capacity ratio capacity is 178F/g, and efficiency E is 99.4%.
Embodiment 4
The present embodiment provides a kind of preparation method of Graphene, is to make by following steps:
1) graphite is added in hydrogen peroxide solution, temperature of reaction is 80 DEG C, stirs 2h, and 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.In described hydrogen peroxide solution, be added with suds-stabilizing agent, 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 further strengthens;
3) by 2) ultrasonic concussion 40min under product normal temperature.Ultrasonic concussion effect makes graphite flake layer by layer apart from further strengthening;
4) by 3) product is added in hydrogen peroxide solution, stirs 6h, and stirring velocity is 300 turn/min, and temperature of reaction is 95 DEG C.Peel off by a hydrogen peroxide intercalation again, graphite flake layer is thoroughly separated, generate Graphene;
5) by 4) product at 80 DEG C, after vacuum-drying 20h, obtain Graphene.
The lamellar spacing of the Graphene making 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 calculating capacity ratio capacity is 146F/g, and efficiency E is 99.3%.
Embodiment 5
The present embodiment provides a kind of preparation method of Graphene, is to make by following steps:
1) graphite is added in hydrogen peroxide solution, temperature of reaction is 75 DEG C, stirs 4h, and 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.In described hydrogen peroxide solution, be added with suds-stabilizing agent, 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 further strengthens;
3) by 2) ultrasonic concussion 50min under product normal temperature.Ultrasonic concussion effect makes graphite flake layer by layer apart from further strengthening;
4) by 3) product is added in hydrogen peroxide solution, stirs 4h, and stirring velocity is 300 turn/min, and temperature of reaction is 105 DEG C.Peel off by a hydrogen peroxide intercalation again, graphite flake layer is thoroughly separated, generate Graphene;
5) by 4) product at 90 DEG C, after vacuum-drying 18h, obtain Graphene.
The lamellar spacing of the Graphene making 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 calculating capacity ratio capacity is 158F/g, and efficiency E is 99.4%.
Although embodiment of the present invention are open as above, but it is not restricted to listed utilization in specification sheets and embodiment, 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 make 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) the ultrasonic concussion of product 30min～1h;
4) by 3) product is added in hydrogen peroxide solution, stirs 2h～8h;
5) by 4) obtain Graphene after product vacuum-drying 12h～24h.
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, in described hydrogen peroxide solution, is added with suds-stabilizing agent, 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 turn/min.
7. the preparation method of Graphene according to claim 1, is characterized in that step 3) ultrasonic concussion 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 to carry out at 60 DEG C～120 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN110697796A (en) * | 2019-10-09 | 2020-01-17 | 福建江夏学院 | Green and efficient synthesis method of transition metal oxyhydroxide ultrathin nanosheets |
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| 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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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110697796A (en) * | 2019-10-09 | 2020-01-17 | 福建江夏学院 | Green and efficient synthesis method of transition metal oxyhydroxide ultrathin nanosheets |
| 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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