CN103896258A - Preparation method for boron-doped graphene - Google Patents
Preparation method for boron-doped graphene Download PDFInfo
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- CN103896258A CN103896258A CN201210574037.6A CN201210574037A CN103896258A CN 103896258 A CN103896258 A CN 103896258A CN 201210574037 A CN201210574037 A CN 201210574037A CN 103896258 A CN103896258 A CN 103896258A
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Abstract
The invention belongs to the field of graphene, and discloses a preparation method for boron-doped graphene. The preparation method comprises steps: adding graphite oxide into a solvent to perform ultrasonic dispersing processing, so as to form a uniformly-dispersed graphene oxide solution with a concentration of 0.5-1 mg/mL; then adding a boron source, stirring to uniformly mixing the two substances and further to obtain a mixed solution of graphene oxide and the boron source; and putting the mixed solution in a reactor, sealing, performing hot pressing treatment at 240 DEG C-400 DEG C and under a pressure of 5-25 MPa for 0.5-5 h, and then releasing the pressure of the reactor to obtain the boron-doped graphene. According to the provided preparation method for boron-doped graphene, graphene oxide and the boron source are relatively uniformly mixed through a liquid phase, then through the pressure instantly released by the critical fluid, the Van der Waal 's force between layers of graphene is destroyed, thus agglomeration of graphene is prevented, and therefore the boron-doped graphene of which graphene and the boron source are mixed uniformly is obtained.
Description
Technical field
The present invention relates to Graphene field, relate in particular to a kind of preparation method of boron doped graphene.
Background technology
Since the strong K sea nurse of the peace moral of Univ Manchester UK (Andre K.Geim) etc. was prepared grapheme material in 2004, because being subject to people, its unique structure and photoelectric property pay attention to widely.Mono-layer graphite is due to its large specific surface area, good conduction, heat conductivility and low thermal expansivity and be considered to desirable material.As: 1. high strength, Young molar weight, (1,100GPa), breaking tenacity: (125GPa); 2. high heat conductance, (5,000W/mK); 3. high conductivity, carrier transport rate, (200,000cm2/Vs); 4. high specific surface area, (calculated value: 2,630m
2/ g).Especially its high conductivity matter, the textural property of large specific surface character and the nanoscale of its unimolecular layer two dimension can be used as electrode materials in ultracapacitor and lithium ion battery.Up to the present, the method of preparing Graphene has many kinds, wherein oxidation-reduction method is a kind ofly can prepare in a large number Graphene and a kind of higher method of productive rate, whole process relates to graphite oxidation is become to graphite oxide, graphite oxide peels off the graphene oxide of generation, then is Graphene by chemistry or thermal reduction.
In the time that graphite oxide is reduced into Graphene, general oxygen level is also in 10% left and right, as electrode materials, make its specific conductivity and electrochemical stability aspect have certain restriction, after oxygen is replaced with boron, the Graphene of the P doping generating, not only can improve its stability, has also obtained enhancing aspect conductivity.
The general direct method by solid boron source or gas boron source and graphite oxide heating is prepared boron doped graphene, makes boron source even not with mixing of Graphene.
Summary of the invention
Problem to be solved by this invention is to provide the boron doped graphene preparation method that mix of a kind of boron source with Graphene.
The preparation method of a kind of boron doped graphene provided by the invention, can make Graphene mix comparatively uniformly with boron source, and the boron doped Graphene of preparation is not easy to reunite.By graphite oxide and solid boron source is first ultrasonic by liquid phase, reach more uniformly and disperse, then mixing solutions is put into high-temperature high-pressure reaction kettle, and then heating and pressurizing is to the critical temperature of solvent, after reaction certain hour, lays down pressure, obtain the thick product of boron doped graphene, then repeatedly rinse by ethanol, filter, the dry boron doped graphene that obtains.
Concrete technical scheme is as follows:
A preparation method for boron doped graphene, comprises the steps:
Graphite oxide is joined to ultrasonic dispersion treatment in solvent, form the homodisperse graphene oxide solution of 0.5-1mg/ml, then add boron source solution, stir process, mixes both, obtains the mixing solutions in graphene oxide and boron source;
Described mixing solutions is put into reactor, after sealing, under 240 DEG C-400 DEG C and 5-25MPa, heat-treat 0.5-5h, lay down the pressure of reactor, to boron doped graphene.
The preparation method of described boron doped graphene, preferably, described solvent is water, ethanol or DMF (DMF).
The preparation method of described boron doped graphene, preferably, the time of described ultrasonic dispersion treatment is 30min-2h.
The preparation method of described boron doped graphene, preferably, described boron source solution is that mass percent is boric acid solution or the boron trioxide solution of 30%-60%, in described boric acid solution and boron trioxide solution, solvent is water, ethanol, N, N-dimethyl pyrrolidone; The mass ratio in the boron source in described graphite oxide and boron source solution is 1:1-3:1.
The preparation method of described boron doped graphene, preferably, described reactor is high-temperature high-pressure reaction kettle.
The preparation method of described boron doped graphene, preferably, after described thermal treatment, also the boron doped graphene making is carried out to purifying drying treatment: the product obtaining after hot-pressing processing ethanol is repeatedly rinsed, filtered, vacuum-drying at 60 DEG C subsequently, obtains the boron doped graphene of purifying.
Boron doped graphene preparation method provided by the invention, by graphene oxide being mixed with boron source in liquid phase, mix comparatively even, again by the pressure of critical fluids abrupt release, destroy Graphene Van der Waals force between layers, prevent the reunion of Graphene, thereby obtain the boron doped graphene that Graphene mixes with boron source; Meanwhile, the boron doped graphene that this method makes has good specific conductivity.
Brief description of the drawings
Fig. 1 is the SEM figure of the boron doped graphene that makes of embodiment 1.
Embodiment
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1
Preparation method is as follows for a kind of boron doped graphene of the present invention:
(1) mixing solutions of graphene oxide and boron trioxide: by the graphite oxide ultrasonic dispersion 0.5h that is added to the water, form the homodisperse graphene oxide solution of 1mg/ml, then adding mass percent is that (boron trioxide joins in the aqueous solution the 30% boron trioxide aqueous solution, after ultrasonic 10 minutes, obtain), stir 10 minutes, both are mixed, obtain the mixing solutions of graphene oxide and boron trioxide; The mass ratio of the boron trioxide in graphite oxide and boron source solution is 1:1.
(2) boron doped Graphene: mixing solutions in obtained (1) is put into high-temperature high-pressure reaction kettle, by its good seal, then be heated to 180 DEG C, reaction 30min, then be heated 400 DEG C, pressure is under 25MPa, keep 60min, slowly lay down the pressure in reactor, obtain boron doped graphene head product, then head product is joined to massfraction and be in 10% hydrochloric acid, to remove remaining boron trioxide, then repeatedly rinse with ethanol, filter, 60 DEG C of vacuum-dryings, obtain boron doped graphene.
Fig. 1 is the SEM figure of the boron doped graphene that makes of embodiment 1.As shown in Figure 1, boron doped graphene has certain fold, there is no and occurs reuniting.
Embodiment 2
Preparation method is as follows for a kind of boron doped graphene of the present invention:
(1) mixing solutions of graphene oxide and boric acid: graphite oxide is joined to ultrasonic dispersion 1h in ethanolic soln, form the homodisperse graphene oxide solution of 0.8mg/ml, then adding mass percent is that (boric acid joins in ethanolic soln 40% boric acid aqueous solution, within ultrasonic 20 minutes, obtain), stir 8 minutes, both are mixed, obtain the mixing solutions of graphene oxide and boric acid; Wherein, the mass ratio of the boric acid in graphite oxide and boron source solution is 2:1.
(2) boron doped Graphene: mixing solutions in obtained (1) is put into high-temperature high-pressure reaction kettle, by its good seal, then be heated 245 DEG C, pressure, under 7MPa, keeps 30min, lay down the pressure in reactor, obtain boron doped graphene head product, this is rinsed repeatedly with ethanol, filter, 60 DEG C of vacuum-dryings, obtain boron doped graphene.
Embodiment 3
Preparation method is as follows for a kind of boron doped graphene of the present invention:
(1) mixing solutions of graphene oxide and boric acid: graphite oxide is joined to ultrasonic dispersion 2h in nmp solvent, form the homodisperse graphene oxide solution of 0.5mg/ml, then adding mass percent is that (boric acid joins NMP(N to 60% boric acid solution, N-dimethyl pyrrolidone) in solvent, within ultrasonic 30 minutes, obtain), stir 5 minutes, both are mixed, obtain the mixing solutions of graphene oxide and boric acid; Wherein, the mass ratio of the boric acid in graphite oxide and boron source solution is 3:1.
(2) boron doped Graphene: mixing solutions in obtained (1) is put into high-temperature high-pressure reaction kettle, by its good seal, then be heated 400 DEG C, pressure, under 5MPa, keeps 10min, lay down the pressure in reactor, obtain boron doped graphene head product, this is rinsed repeatedly with ethanol, filter, 60 DEG C of vacuum-dryings, obtain boron doped graphene.
The specific conductivity test of boron doped graphene
The specific conductivity of measuring boron doped Graphene by four probe method, test result is as shown in table 1.From conductivity data, the specific conductivity of prepared boron doped graphene is higher.
Table 1
| Embodiment | 1 | 2 | 3 |
| Specific conductivity (S/m) | 9.63×10 4 | 9.57×10 4 | 9.42×10 4 |
Should be understood that, the above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, and scope of patent protection of the present invention should be as the criterion with claims.
Claims (7)
1. a preparation method for boron doped graphene, is characterized in that, comprises the steps:
Graphite oxide is joined to ultrasonic dispersion treatment in solvent, form the homodisperse graphene oxide solution of 0.5-1mg/ml, then add boron source solution, stir process, mixes both, obtains the mixing solutions in graphene oxide and boron source;
Described mixing solutions is put into reactor, after sealing, under 240 DEG C-400 DEG C and 5-25MPa, carry out hot-pressing processing 0.5-5h, lay down the pressure of reactor, obtain boron doped graphene.
2. the preparation method of boron doped graphene according to claim 1, is characterized in that, described solvent is water, ethanol or DMF.
3. the preparation method of boron doped graphene according to claim 1, is characterized in that, the time of described ultrasonic dispersion treatment is 30min-2h.
4. the preparation method of boron doped graphene according to claim 1, is characterized in that, described boron source solution is that mass percent is boric acid solution or the boron trioxide solution of 30%-60%; The mass ratio in the boron source in described graphite oxide and described boron source solution is 1:1-3:1.
5. the preparation method of boron doped graphene according to claim 1, is characterized in that, in described boric acid solution and boron trioxide solution, solvent is water, ethanol, N, N-dimethyl pyrrolidone.
6. the preparation method of boron doped graphene according to claim 1, is characterized in that, described reactor is high-temperature high-pressure reaction kettle.
7. the preparation method of boron doped graphene according to claim 1, it is characterized in that, after described hot-pressing processing, also the boron doped graphene making is carried out to purifying drying treatment: the product obtaining after hot-pressing processing ethanol is repeatedly rinsed, filtered, vacuum-drying at 60 DEG C subsequently, obtains the boron doped graphene of purifying.
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| CN106430175A (en) * | 2016-11-07 | 2017-02-22 | 山东欧铂新材料有限公司 | Rapid preparation methods of graphene oxide and graphene |
| CN106564891A (en) * | 2016-11-07 | 2017-04-19 | 山东欧铂新材料有限公司 | Preparing method of oxidized graphene and high-conductivity graphene |
| CN107300579A (en) * | 2017-08-08 | 2017-10-27 | 肇庆高新区长光智能技术开发有限公司 | A kind of domestic carbon monoxide detection means |
| CN108568277A (en) * | 2018-04-16 | 2018-09-25 | 武汉工程大学 | The preparation method of boron doping graphene/polypyrrole composite aerogel with compression and back renaturation |
| CN108711522A (en) * | 2018-04-26 | 2018-10-26 | 武汉工程大学 | A kind of boron doping graphene/polyaniline composite aerogel and preparation method thereof |
| CN111377457A (en) * | 2020-03-22 | 2020-07-07 | 安徽大学 | Boron-adsorption graphene nano material and preparation method thereof |
| CN111944267A (en) * | 2020-07-30 | 2020-11-17 | 山东大学 | Preparation method of boron-doped graphene composite material and application of boron-doped graphene composite material as negative dielectric material |
| CN112877562A (en) * | 2021-01-14 | 2021-06-01 | 中国航空制造技术研究院 | Boron-doped graphene reinforced copper-based composite material and preparation method thereof |
| CN116387482A (en) * | 2023-03-30 | 2023-07-04 | 湖南金阳烯碳新材料股份有限公司 | Graphene anode material and preparation method thereof |
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| CN106564891A (en) * | 2016-11-07 | 2017-04-19 | 山东欧铂新材料有限公司 | Preparing method of oxidized graphene and high-conductivity graphene |
| CN106430175A (en) * | 2016-11-07 | 2017-02-22 | 山东欧铂新材料有限公司 | Rapid preparation methods of graphene oxide and graphene |
| CN107300579A (en) * | 2017-08-08 | 2017-10-27 | 肇庆高新区长光智能技术开发有限公司 | A kind of domestic carbon monoxide detection means |
| CN108568277A (en) * | 2018-04-16 | 2018-09-25 | 武汉工程大学 | The preparation method of boron doping graphene/polypyrrole composite aerogel with compression and back renaturation |
| CN108568277B (en) * | 2018-04-16 | 2021-06-01 | 武汉工程大学 | Preparation method of boron-doped graphene/polypyrrole composite aerogel with compression resilience |
| CN108711522A (en) * | 2018-04-26 | 2018-10-26 | 武汉工程大学 | A kind of boron doping graphene/polyaniline composite aerogel and preparation method thereof |
| CN111377457B (en) * | 2020-03-22 | 2022-02-08 | 安徽大学 | Boron-adsorption graphene nano material and preparation method thereof |
| CN111377457A (en) * | 2020-03-22 | 2020-07-07 | 安徽大学 | Boron-adsorption graphene nano material and preparation method thereof |
| CN111944267A (en) * | 2020-07-30 | 2020-11-17 | 山东大学 | Preparation method of boron-doped graphene composite material and application of boron-doped graphene composite material as negative dielectric material |
| CN111944267B (en) * | 2020-07-30 | 2021-06-29 | 山东大学 | Preparation method of boron-doped graphene composite material and application of boron-doped graphene composite material as negative dielectric material |
| CN112877562A (en) * | 2021-01-14 | 2021-06-01 | 中国航空制造技术研究院 | Boron-doped graphene reinforced copper-based composite material and preparation method thereof |
| CN112877562B (en) * | 2021-01-14 | 2022-03-04 | 中国航空制造技术研究院 | Boron-doped graphene reinforced copper-based composite material and preparation method thereof |
| CN116387482A (en) * | 2023-03-30 | 2023-07-04 | 湖南金阳烯碳新材料股份有限公司 | Graphene anode material and preparation method thereof |
| CN116387482B (en) * | 2023-03-30 | 2024-05-07 | 湖南金阳烯碳新材料股份有限公司 | Graphene anode material and preparation method thereof |
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