CN105366668A - Method for preparing graphene through supercritical fluid - Google Patents
Method for preparing graphene through supercritical fluid Download PDFInfo
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- CN105366668A CN105366668A CN201510740191.XA CN201510740191A CN105366668A CN 105366668 A CN105366668 A CN 105366668A CN 201510740191 A CN201510740191 A CN 201510740191A CN 105366668 A CN105366668 A CN 105366668A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention discloses a method for preparing graphene through supercritical fluid. The method includes the first step of expansion preprocessing of graphene, wherein the graphene is placed in a mixed solution composed of an oxidizing agent and an intercalator and stirred at the temperature of 20-60 DEG C, an obtained product is washed, filtered, dried and placed in a muffle furnace, the product is processed in an air atmosphere at the high temperature of 600-1200 DEG C, and an expanded graphene product is obtained for use; the second step of preparation of the graphene, wherein the obtained product is added into a polytetrafluoroethylene container, the supercritical fluid is injected, the temperature is adjusted to be 40-160 DEG C, the pressure strength is adjusted to 5-30 MPa, the supercritical fluid is in a supercritical state, gas is exhausted through an exhaust valve after the reactant is reacted under the magnetic stirring condition, a reacting product is taken out, a certain amount of dispersing solvent is then added, the reacting product is diffused again through ultrasonic and stirring, after the product is centrifuged to obtain supernate, and the graphene is prepared. The reaction process is simple, the price is low, large-scale production is easy, and the graphene prepared through the method is small in impurity content, small in number of layers and thin.
Description
Technical field
The present invention relates to field of novel technology, a kind of method of preparing graphene by using supercritical fluid is particularly provided.
Background technology
The preparation method of Graphene is the hot issue that people pay close attention to always, and synthetic method main at present has mechanical stripping method, epitaxial growth method, chemical gas phase to sink to the bottom and liquid-phase oxidation reduction method etc.Although first three kind scheme can obtain high-quality Graphene, equipment investment is comparatively large, and cost is higher; And although liquid-phase oxidation reduction method cost is lower, complex steps, magazine content is high, and uses a large amount of highly basic, Strong oxdiative, strong reducible agent, and environmental pollution is serious.A kind of clean, pollution-free, cheap and high efficiency dispersion medium of abundance of supercutical fluid.
Summary of the invention
In view of this, the present invention is directed to the disappearance of prior art existence, the object of the present invention is to provide a kind of method of preparing graphene by using supercritical fluid, its reaction process is simple, cheap, be easy to scale operation, and Graphene foreign matter content obtained by the method is few, the number of plies is low, thickness is thin.
For achieving the above object, the present invention adopts following technical scheme: a kind of method of preparing graphene by using supercritical fluid, includes following steps:
1) the expansion pre-treatment of graphite:
Graphite is placed in the mixing solutions be made up of oxygenant and intercalator, stir process 0.5 ~ 5h at 20 ~ 60 DEG C, the product obtained is placed in retort furnace through washing, filtration, drying, processes 3 ~ 60s, obtain expanded graphite product for subsequent use in air atmosphere and under 600 ~ 1200 DEG C of high temperature;
2) preparation of Graphene:
Add in polytetrafluoroethylcontainer container by above-mentioned products therefrom, put into autoclave after sealing, upper cover seals; Inject supercutical fluid, regulating temperature to be 40 ~ 160 DEG C and pressure is 5 ~ 30MPa, supercutical fluid is wherein made to reach supercritical state, after reactant reacts 1 ~ 24h under magnetic stirring, exitted by snifting valve, take out reaction product, then add a certain amount of dispersion solvent, carry out redispersion by ultrasonic and stirring, get supernatant liquor after product is centrifugal and obtained Graphene.
As a kind of preferred version, described graphite raw material is synthetic graphite or natural graphite; Described oxygenant is one or more in the vitriol oil, hydrogen peroxide, potassium permanganate, perchloric acid, concentrated nitric acid; Described intercalator is dimethyl formamide, methyl-2-pyrrolidone, methylacetamide, Sodium dodecylbenzene sulfonate or methyl-sulphoxide.
As a kind of preferred version, described graphite: oxygenant: the mass ratio of intercalator is 1:0.5 ~ 10:0.5 ~ 10.
As a kind of preferred version, it is 1 ~ 10g/L that described expanded graphite adds concentration.
As a kind of preferred version, described supercutical fluid is carbonic acid gas, ethanol, ethane or water.
As a kind of preferred version, described dispersion solvent is dimethyl formamide, methyl-2-pyrrolidone, ethanol, Virahol, acetone or water.
The present invention compared with prior art has obvious advantage and beneficial effect, is specially:
1, the inventive method is by utilize supercritical fluid method to prepare foreign matter content is few, the number of plies is low, thickness is about 0.3 ~ 3nm high-quality Graphene, and it has good electric property.The number of plies of gained Graphene can regulate by regulating intercalator and the consumption of oxygenant, the concentration of supercritical fluids system and splitting time.
2, the present invention is by carrying out preexpanding process to graphite raw material, not only expands the scope of application of the method, and can in a big way in realize adjustment to the Graphene number of plies, gained Graphene is more easily dispersed in water and various organic solvent, applied widely.
3, the supercutical fluid that the inventive method uses has the advantages such as price is low, environmental pollution is little, can be recycled.
Embodiment
Embodiment 1
A method for preparing graphene by using supercritical fluid, includes following steps:
1) the expansion pre-treatment of graphite:
Graphite is placed in the mixing solutions be made up of oxygenant and intercalator, stir process 5h at 20 DEG C, the product obtained is placed in retort furnace through washing, filtration, drying, processes 3s, obtain expanded graphite product for subsequent use in air atmosphere and under 1200 DEG C of high temperature;
2) preparation of Graphene:
Add in polytetrafluoroethylcontainer container by above-mentioned products therefrom, put into autoclave after sealing, upper cover seals; Inject supercutical fluid, regulating temperature to be 160 DEG C and pressure is 5MPa, makes supercutical fluid wherein reach supercritical state, after reactant reacts 24h under magnetic stirring, exitted by snifting valve, take out reaction product, then add a certain amount of dimethyl formamide, carry out redispersion by ultrasonic and stirring, supernatant liquor is got after product is centrifugal, remove the graphite granule be not stripped, supernatant liquor removes possible impurity through pickling, extraction etc., both obtains the stable dispersion solution of Graphene.Also as required, the stable dispersions of above-mentioned Graphene can be obtained solid graphite ene product through vacuum drying treatment.
This graphite raw material is synthetic graphite; This oxygenant is the vitriol oil; This intercalator is dimethyl formamide; This graphite: oxygenant: the mass ratio of intercalator is 1:1:0.5.This supercutical fluid is water; It is 1g/L that this expanded graphite adds concentration.
Embodiment 2
A method for preparing graphene by using supercritical fluid, includes following steps:
1) the expansion pre-treatment of graphite:
Graphite is placed in the mixing solutions be made up of oxygenant and intercalator, stir process 5h at 60 DEG C, the product obtained is placed in retort furnace through washing, filtration, drying, processes 60s, obtain expanded graphite product for subsequent use in air atmosphere and under 600 DEG C of high temperature;
2) preparation of Graphene:
Add in polytetrafluoroethylcontainer container by above-mentioned products therefrom, put into autoclave after sealing, upper cover seals; Inject supercutical fluid, regulating temperature to be 40 DEG C and pressure is 30MPa, makes supercutical fluid wherein reach supercritical state, after reactant reacts 1h under magnetic stirring, exitted by snifting valve, take out reaction product, then add a certain amount of methyl-2-pyrrolidone, carry out redispersion by ultrasonic and stirring, supernatant liquor is got after product is centrifugal, remove the graphite granule be not stripped, supernatant liquor removes possible impurity through pickling, extraction etc., both obtains the stable dispersion solution of Graphene.Also as required, the stable dispersions of above-mentioned Graphene can be obtained solid graphite ene product through vacuum drying treatment.
This graphite raw material is natural graphite; This oxygenant is hydrogen peroxide; This intercalator is methyl-2-pyrrolidone, this graphite: oxygenant: the mass ratio of intercalator is 1:0.5:3; This supercutical fluid is ethanol; It is 10g/L that this expanded graphite adds concentration.
Embodiment 3
A method for preparing graphene by using supercritical fluid, includes following steps:
1) the expansion pre-treatment of graphite:
Graphite is placed in the mixing solutions be made up of oxygenant and intercalator, stir process 4h at 40 DEG C, the product obtained is placed in retort furnace through washing, filtration, drying, processes 40s, obtain expanded graphite product for subsequent use in air atmosphere and under 800 DEG C of high temperature;
2) preparation of Graphene:
Add in polytetrafluoroethylcontainer container by above-mentioned products therefrom, put into autoclave after sealing, upper cover seals; Inject supercutical fluid, regulating temperature to be 100 DEG C and pressure is 20MPa, makes supercutical fluid wherein reach supercritical state, after reactant reacts 14h under magnetic stirring, exitted by snifting valve, take out reaction product, then add a certain amount of ethanol, carry out redispersion by ultrasonic and stirring, supernatant liquor is got after product is centrifugal, remove the graphite granule be not stripped, supernatant liquor removes possible impurity through pickling, extraction etc., both obtains the stable dispersion solution of Graphene.Also as required, the stable dispersions of above-mentioned Graphene can be obtained solid graphite ene product through vacuum drying treatment.
This graphite raw material is natural graphite; This oxygenant is perchloric acid; This intercalator is methylacetamide; This graphite: oxygenant: the mass ratio of intercalator is 1:5:10; This supercutical fluid is ethane; It is 7g/L that this expanded graphite adds concentration.
Embodiment 4
A method for preparing graphene by using supercritical fluid, includes following steps:
1) the expansion pre-treatment of graphite:
Graphite is placed in the mixing solutions be made up of oxygenant and intercalator, stir process 3h at 50 DEG C, the product obtained is placed in retort furnace through washing, filtration, drying, processes 30s, obtain expanded graphite product for subsequent use in air atmosphere and under 1000 DEG C of high temperature;
2) preparation of Graphene:
Add in polytetrafluoroethylcontainer container by above-mentioned products therefrom, put into autoclave after sealing, upper cover seals; Inject supercutical fluid, regulating temperature to be 130 DEG C and pressure is 18MPa, makes supercutical fluid wherein reach supercritical state, after reactant reacts 18h under magnetic stirring, exitted by snifting valve, take out reaction product, then add a certain amount of water, carry out redispersion by ultrasonic and stirring, supernatant liquor is got after product is centrifugal, remove the graphite granule be not stripped, supernatant liquor removes possible impurity through pickling, extraction etc., both obtains the stable dispersion solution of Graphene.Also as required, the stable dispersions of above-mentioned Graphene can be obtained solid graphite ene product through vacuum drying treatment.
This graphite raw material is synthetic graphite; This oxygenant is concentrated nitric acid; This intercalator is Sodium dodecylbenzene sulfonate; This graphite: oxygenant: the mass ratio of intercalator is 1:10:4; This supercutical fluid is water; It is 5g/L that this expanded graphite adds concentration.
Comparative example 1, employing Conventional graphite material is negative material.
The practical application of embodiment 1 ~ 4 and comparative example, specific as follows:
In mass ratio for 80:10:10 is by active substance (Graphene obtained by employing embodiment 1 ~ 4 or the ordinary graphite of comparative example), acetylene black and polyvinylidene difluoride (PVDF) (PVDF) mixed grinding, drip appropriate N-Methyl pyrrolidone (NMP) solution, agitation and dilution is homogeneous paste, be coated in nickel foam, form negative plate.Pole piece is placed in the vacuum drying oven oven dry of 80 DEG C, on tabletting machine, carries out compressing tablet with the pressure of 10MPa, then pole piece is put into 120 DEG C of dry 12h of vacuum drying oven.Dried pole piece is transferred in glove box, using metal lithium sheet as to electrode, is assembled into simulation button cell in the glove box being full of dry argon gas.Barrier film is porous polypropylene film, and electrolytic solution is the LiPF6 solution of 1mol/L, and wherein electrolyte solvent is the mixed solvent of NSC 11801 (EC) and diethyl carbonate (DEC).
Adopt the power cell Performance comparision obtained by graphite cathode material of embodiment 1 ~ 4 and comparative example as follows:
Of the present inventionly to focus on: the inventive method is by utilize supercritical fluid method to prepare foreign matter content is few, the number of plies is low, thickness is about 0.3 ~ 3nm high-quality Graphene, and it has good electric property.The number of plies of gained Graphene can regulate by regulating intercalator and the consumption of oxygenant, the concentration of supercritical fluids system and splitting time.The present invention, by carrying out preexpanding process to graphite raw material, not only expands the scope of application of the method, and can in a big way in realize adjustment to the Graphene number of plies, gained Graphene is more easily dispersed in water and various organic solvent, applied widely; The supercutical fluid that the inventive method uses has the advantages such as price is low, environmental pollution is little, can be recycled.
The above, it is only preferred embodiment of the present invention, not technical scope of the present invention is imposed any restrictions, thus every according to technical spirit of the present invention to any trickle amendment made for any of the above embodiments, equivalent variations and modification, all still belong in the scope of technical solution of the present invention.
Claims (6)
1. a method for preparing graphene by using supercritical fluid, is characterized in that: include following steps:
1) the expansion pre-treatment of graphite:
Graphite is placed in the mixing solutions be made up of oxygenant and intercalator, stir process 0.5 ~ 5h at 20 ~ 60 DEG C, the product obtained is placed in retort furnace through washing, filtration, drying, processes 3 ~ 60s, obtain expanded graphite product for subsequent use in air atmosphere and under 600 ~ 1200 DEG C of high temperature;
2) preparation of Graphene
Add in polytetrafluoroethylcontainer container by above-mentioned products therefrom, put into autoclave after sealing, upper cover seals; Inject supercutical fluid, regulating temperature to be 40 ~ 160 DEG C and pressure is 5 ~ 30MPa, supercutical fluid is wherein made to reach supercritical state, after reactant reacts 1 ~ 24h under magnetic stirring, exitted by snifting valve, take out reaction product, then add a certain amount of dispersion solvent, carry out redispersion by ultrasonic and stirring, get supernatant liquor after product is centrifugal and obtained Graphene.
2. the method for a kind of preparing graphene by using supercritical fluid according to claim 1, is characterized in that: described graphite raw material is synthetic graphite or natural graphite; Described oxygenant is one or more in the vitriol oil, hydrogen peroxide, potassium permanganate, perchloric acid, concentrated nitric acid; Described intercalator is dimethyl formamide, methyl-2-pyrrolidone, methylacetamide, Sodium dodecylbenzene sulfonate or methyl-sulphoxide.
3. a kind of method of preparing graphene by using supercritical fluid according to claim 1 or 2, is characterized in that: described graphite: oxygenant: the mass ratio of intercalator is 1:0.5 ~ 10:0.5 ~ 10.
4. the method for a kind of preparing graphene by using supercritical fluid according to claim 1, is characterized in that: it is 1 ~ 10g/L that described expanded graphite adds concentration.
5. the method for a kind of preparing graphene by using supercritical fluid according to claim 1, is characterized in that: described supercutical fluid is carbonic acid gas, ethanol, ethane or water.
6. the method for a kind of preparing graphene by using supercritical fluid according to claim 1, is characterized in that: described dispersion solvent is dimethyl formamide, methyl-2-pyrrolidone, ethanol, Virahol, acetone or water.
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Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106044764A (en) * | 2016-08-17 | 2016-10-26 | 新奥科技发展有限公司 | Apparatus and method of supercritically preparing graphene |
| CN106044765A (en) * | 2016-08-17 | 2016-10-26 | 新奥科技发展有限公司 | Apparatus and method of supercritically preparing graphene |
| CN106129343A (en) * | 2016-05-25 | 2016-11-16 | 福建翔丰华新能源材料有限公司 | A kind of preparation method of Graphene titanium dioxide microballoon sphere |
| CN106115666A (en) * | 2016-06-16 | 2016-11-16 | 上海多希石墨烯材料科技有限公司 | A kind of ultrasound wave, supercritical CO2and the method that Graphene is prepared in three strippings of microwave |
| CN106185886A (en) * | 2016-07-01 | 2016-12-07 | 成都新柯力化工科技有限公司 | The method of Graphene and prepared Graphene powder are prepared in a kind of continuous scale |
| CN107399734A (en) * | 2017-08-09 | 2017-11-28 | 福建猛狮新能源科技有限公司 | A kind of high yield fluorinated graphene preparation method |
| CN108017050A (en) * | 2016-11-02 | 2018-05-11 | 中国石油大学(北京) | A kind of doped graphene and its preparation method and application |
| CN108689403A (en) * | 2018-08-30 | 2018-10-23 | 多凌新材料科技股份有限公司 | The method that supercritical fluid auxiliary prepares expansible graphite |
| CN109179390A (en) * | 2018-08-08 | 2019-01-11 | 青岛领军节能与新材料研究院 | A kind of preparation method of high-quality graphene |
| CN110668433A (en) * | 2019-11-25 | 2020-01-10 | 陕西师范大学 | Method for preparing graphite/graphene composite material by supercritical carbon dioxide fluid and application |
| CN110734057A (en) * | 2018-07-19 | 2020-01-31 | 矿物股份有限公司 | Synthesis method of graphene oxide |
| CN111825935A (en) * | 2020-08-11 | 2020-10-27 | 佛山市南海崇泰防火材料有限公司 | Flexible fireproof tube for wires and cables and application thereof |
| CN111907171A (en) * | 2020-08-11 | 2020-11-10 | 佛山市南海崇泰防火材料有限公司 | Improved flexible fire-proof strip and its use |
| CN112209371A (en) * | 2020-10-15 | 2021-01-12 | 北京石墨烯研究院有限公司 | Supercritical preparation method of graphene oxide |
| CN113307258A (en) * | 2021-05-28 | 2021-08-27 | 黑龙江益墨轩新材料科技有限公司 | Preparation method of graphene electric heating plate |
| CN113500053A (en) * | 2021-08-19 | 2021-10-15 | 中国石化中原石油化工有限责任公司 | By using supercritical CO2Method for preparing high-purity polypropylene |
| CN114590804A (en) * | 2022-01-26 | 2022-06-07 | 深圳市翔丰华科技股份有限公司 | Method for efficiently preparing doped graphene through supercritical fluid |
| CN115259143A (en) * | 2022-08-01 | 2022-11-01 | 郑州大学 | Method for preparing ferromagnetic graphene by using supercritical carbon dioxide |
| CN116495727A (en) * | 2023-05-19 | 2023-07-28 | 烟台大学 | Preparation method and application of expanded graphene material by using popcorn machine |
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| CN106129343A (en) * | 2016-05-25 | 2016-11-16 | 福建翔丰华新能源材料有限公司 | A kind of preparation method of Graphene titanium dioxide microballoon sphere |
| CN106129343B (en) * | 2016-05-25 | 2019-07-19 | 福建翔丰华新能源材料有限公司 | A kind of preparation method of graphene-titanium dioxide microballoon sphere |
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| CN106185886A (en) * | 2016-07-01 | 2016-12-07 | 成都新柯力化工科技有限公司 | The method of Graphene and prepared Graphene powder are prepared in a kind of continuous scale |
| CN106044764B (en) * | 2016-08-17 | 2019-02-12 | 新奥科技发展有限公司 | The overcritical device and method for preparing graphene |
| CN106044765A (en) * | 2016-08-17 | 2016-10-26 | 新奥科技发展有限公司 | Apparatus and method of supercritically preparing graphene |
| CN106044764A (en) * | 2016-08-17 | 2016-10-26 | 新奥科技发展有限公司 | Apparatus and method of supercritically preparing graphene |
| CN108017050A (en) * | 2016-11-02 | 2018-05-11 | 中国石油大学(北京) | A kind of doped graphene and its preparation method and application |
| CN107399734A (en) * | 2017-08-09 | 2017-11-28 | 福建猛狮新能源科技有限公司 | A kind of high yield fluorinated graphene preparation method |
| CN110734057B (en) * | 2018-07-19 | 2023-01-10 | 矿物股份有限公司 | Synthesis method of graphene oxide |
| CN110734057A (en) * | 2018-07-19 | 2020-01-31 | 矿物股份有限公司 | Synthesis method of graphene oxide |
| CN109179390A (en) * | 2018-08-08 | 2019-01-11 | 青岛领军节能与新材料研究院 | A kind of preparation method of high-quality graphene |
| CN108689403A (en) * | 2018-08-30 | 2018-10-23 | 多凌新材料科技股份有限公司 | The method that supercritical fluid auxiliary prepares expansible graphite |
| CN110668433A (en) * | 2019-11-25 | 2020-01-10 | 陕西师范大学 | Method for preparing graphite/graphene composite material by supercritical carbon dioxide fluid and application |
| CN111825935A (en) * | 2020-08-11 | 2020-10-27 | 佛山市南海崇泰防火材料有限公司 | Flexible fireproof tube for wires and cables and application thereof |
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| CN112209371A (en) * | 2020-10-15 | 2021-01-12 | 北京石墨烯研究院有限公司 | Supercritical preparation method of graphene oxide |
| CN113307258A (en) * | 2021-05-28 | 2021-08-27 | 黑龙江益墨轩新材料科技有限公司 | Preparation method of graphene electric heating plate |
| CN113500053A (en) * | 2021-08-19 | 2021-10-15 | 中国石化中原石油化工有限责任公司 | By using supercritical CO2Method for preparing high-purity polypropylene |
| CN114590804A (en) * | 2022-01-26 | 2022-06-07 | 深圳市翔丰华科技股份有限公司 | Method for efficiently preparing doped graphene through supercritical fluid |
| CN115259143A (en) * | 2022-08-01 | 2022-11-01 | 郑州大学 | Method for preparing ferromagnetic graphene by using supercritical carbon dioxide |
| CN116495727A (en) * | 2023-05-19 | 2023-07-28 | 烟台大学 | Preparation method and application of expanded graphene material by using popcorn machine |
| CN116495727B (en) * | 2023-05-19 | 2024-01-23 | 烟台大学 | Preparation method and application of expanded graphene material by using popcorn machine |
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