CN103896258B - A kind of preparation method of boron doped graphene - Google Patents
A kind of preparation method of boron doped graphene Download PDFInfo
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- CN103896258B CN103896258B CN201210574037.6A CN201210574037A CN103896258B CN 103896258 B CN103896258 B CN 103896258B CN 201210574037 A CN201210574037 A CN 201210574037A CN 103896258 B CN103896258 B CN 103896258B
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Abstract
The invention belongs to field of graphene, it discloses a kind of preparation method of boron doped graphene, comprise step: graphite oxide is joined ultrasonic disperse process in solvent, form the homodisperse graphene oxide solution of 0.5-1mg/ml, then boron source is added, stir process, makes both mix, 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, carries out hot-pressing processing 0.5-5h, lay down the pressure of reactor, obtain boron doped graphene.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, thus obtain the boron doped graphene that Graphene mixes with boron source.
Description
Technical field
The present invention relates to field of graphene, particularly relate to a kind of preparation method of boron doped graphene.
Background technology
Since strong K sea nurse (AndreK.Geim) of the peace moral of Univ Manchester UK etc. prepared grapheme material in 2004, pay attention to widely because the structure of its uniqueness and photoelectric property receive people.Mono-layer graphite due to its large specific surface area, excellent 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 connductivity character, the textural property of the nanoscale of large specific surface character and its unimolecular layer two dimension, can be used as electrode materials in ultracapacitor and lithium ion battery.Up to the present, the method preparing Graphene has many kinds, wherein oxidation-reduction method a kind ofly can prepare Graphene in a large number and a kind of higher method of productive rate, whole process relates to and graphite oxidation is become graphite oxide, graphite oxide peels off the graphene oxide of generation, then is Graphene by chemistry or thermal reduction.
When graphite oxide is reduced into Graphene, general oxygen level is also about 10%, as electrode materials, its specific conductivity and electrochemical stability aspect is made to have certain restriction, when oxygen with boron replace after, the Graphene of the P doping generated, not only can improve its stability, in conductivity, have also been obtained enhancing.
Generally the direct method heated by solid boron source or gas boron source and graphite oxide prepares 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.It is ultrasonic by graphite oxide and solid boron source are first passed through liquid phase, reach and disperse more uniformly, 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, lay down pressure, obtain the thick product of boron doped graphene, then repeatedly rinsed by ethanol, filter, drying obtains boron doped graphene.
Concrete technical scheme is as follows:
A preparation method for boron doped graphene, comprises the steps:
Graphite oxide is joined ultrasonic disperse process in solvent, form the homodisperse graphene oxide solution of 0.5-1mg/ml, then add boron source solution, stir process, make both mix, obtain 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-treats 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 disperse process is 30min-2h.
The preparation method of described boron doped graphene, preferably, boric acid solution or the boron trioxide solution of described boron source solution to be mass percent be 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 purifying drying treatment is carried out to obtained boron doped graphene: the product ethanol obtained after hot-pressing processing 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, thus obtain the boron doped graphene that Graphene mixes with boron source; Meanwhile, the boron doped graphene that this method is obtained has good specific conductivity.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the boron doped graphene that embodiment 1 obtains.
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: be added to the water graphite oxide ultrasonic disperse 0.5h, 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, obtain after ultrasonic 10 minutes), stir 10 minutes, make both mix, 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 180 DEG C are heated to, reaction 30min, then 400 DEG C are heated, pressure is under 25MPa, keep 60min, slowly lay down the pressure in reactor, obtain boron doped graphene head product, then head product being joined massfraction is in the hydrochloric acid of 10%, 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 embodiment 1 obtains.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 ultrasonic disperse 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, make both mix, 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 ultrasonic disperse 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, make both mix, 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
Measured the specific conductivity of 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 present pre-ferred embodiments is comparatively detailed, and therefore can not think the restriction to scope of patent protection of the present invention, scope of patent protection of the present invention should be as the criterion with claims.
Claims (6)
1. a preparation method for boron doped graphene, is characterized in that, comprises the steps:
Graphite oxide is joined ultrasonic disperse process in solvent, form the homodisperse graphene oxide solution of 0.5-1mg/ml, then add boron source solution, stir process, make both mix, obtain 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, carries out hot-pressing processing 0.5-5h, lay down the pressure of reactor, obtain boron doped graphene, wherein, boric acid solution or the boron trioxide solution of described boron source solution to be mass percent be 30%-60%; The mass ratio in the boron source in described graphite oxide and described boron source solution is 1:1-3:1.
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 disperse process is 30min-2h.
4. 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.
5. the preparation method of boron doped graphene according to claim 1, is characterized in that, described reactor is high-temperature high-pressure reaction kettle.
6. the preparation method of boron doped graphene according to claim 1, it is characterized in that, after described hot-pressing processing, also purifying drying treatment is carried out to obtained boron doped graphene: the product ethanol obtained after hot-pressing processing is repeatedly rinsed, filtered, vacuum-drying at 60 DEG C subsequently, obtains the boron doped graphene of purifying.
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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| 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 |
| CN108711522B (en) * | 2018-04-26 | 2020-10-23 | 武汉工程大学 | Boron-doped 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 |
| 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 |
| 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 |
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