CN103449408A - Boron doped graphene and preparation method thereof - Google Patents
Boron doped graphene and preparation method thereof Download PDFInfo
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- CN103449408A CN103449408A CN2012101713628A CN201210171362A CN103449408A CN 103449408 A CN103449408 A CN 103449408A CN 2012101713628 A CN2012101713628 A CN 2012101713628A CN 201210171362 A CN201210171362 A CN 201210171362A CN 103449408 A CN103449408 A CN 103449408A
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Abstract
The invention belongs to the technology field of graphene materials, and discloses a boron doped graphene and a preparation method thereof. The invention adopts a high temperature hot doping method to prepare boron doped graphene. The method comprises following steps: taking graphite as the raw material, and oxidizing the graphite so as to obtain graphite oxide; placing the graphite oxide in a mixed gas atmosphere composed of inert gas and boron source gas, heating to the temperature of 800 to 1100 DEG C, then maintaining the temperature for 0.5 to 2 hours, and cooling the product to the room temperature so as to obtain boron doped graphene. The technology by utilizing the high temperature hot doping method to prepare boron doped graphene has the advantages of few steps, simple operation, and low requirements on equipment, and is benefit for mass industrial production. Graphite oxide is a carbon material with a preferably bad ordering, the material with a lower ordering is more suitable for carrying out boron doping, and the doping process is more homogenous by adopting gas state boron source. The prepared boron doped graphene presents a P-type doping, because the original conjugated structure of graphene is not affected, the boron doped graphene has a more excellent conductive performance than that of graphene.
Description
Technical field
The present invention relates to the grapheme material technical field, more specifically, relate to a kind of boron doped graphene and preparation method thereof.
Background technology
Graphene is a kind ofly by carbon atom, with the sp2 hybridized orbital, to form the flat film that hexangle type is the honeycomb lattice, is the two-dimensional material of only having a carbon atom thickness.Since within 2004, being found, Graphene is subject to showing great attention to of industry-by-industry due to its two-dimentional unit molecule structure and good physical properties.It has high theoretical specific surface area, good physical strength, good snappiness and high conductivity etc., can be applicable to matrix material, battery electrode material, hydrogen storage material, field emmision material and hypersensitization sensor technical field, bring change will to the material in the fields such as electronics, the energy.
Boron doped graphene and nitrogen-doped graphene are two kinds of representational Graphene derivatives.Wherein, due to the outer few electronics of boron atom ratio carbon atom, the boron doped graphene is the doping of P-type, therefore at semi-conductor and energy storage material field, has broad application prospects.At present, the main method for preparing the boron doped graphene is chemical Vapor deposition process and arc discharge method.But these two kinds of methods all relate to precision equipment and complex operations, more difficultly realize preparation of industrialization.
Summary of the invention
The technical problem to be solved in the present invention is, high for the equipment of the chemical Vapor deposition process for preparing the boron doped graphene in prior art and arc discharge method and operational requirement, as to be difficult to realize preparation of industrialization defect, provide a kind of low for equipment requirements, simple to operate, processing efficiency is high and be convenient to realize the preparation method of boron doped graphene prepared by large-scale industry.
Another technical problem that the present invention will solve is, a kind of boron doped graphene is provided, and this Graphene derivative has the conductivity more excellent than Graphene.
The technical problem to be solved in the present invention is achieved by the following technical programs: according to an aspect of the present invention, provide a kind of preparation method of boron doped graphene, adopt the standby described boron doped graphene of high temperature hot doping legal system, said method comprising the steps of:
S1: prepare graphite oxide: take graphite as raw material, make graphite oxide after oxidation; And
S2: prepare described boron doped graphene: the mixed gas atmosphere that described graphite oxide is placed in to rare gas element and boron source gas formation, being warming up to 800～1100 ℃ also is incubated and processes 0.5～2 hour, products therefrom is cooled to room temperature, obtains described boron doped graphene.
In the preparation method of above-mentioned boron doped graphene, in described step S1, the purity of described graphite is 99.5%.
In the preparation method of above-mentioned boron doped graphene, described step S1 comprises: load weighted graphite is added in the mixing solutions of the vitriol oil and concentrated nitric acid, mix in bath and stir at frozen water, in mixing solutions, add again potassium permanganate to make the preliminary oxidation of graphite, then mixing solutions is heated to 70～95 ℃, insulation is processed and is made the further oxidation of graphite, in mixing solutions, add again hydrogen peroxide to remove potassium permanganate, suction filtration also carries out repetitive scrubbing with dilute hydrochloric acid and deionized water to products therefrom, makes described graphite oxide after drying.
In the preparation method of above-mentioned boron doped graphene, the mass volume ratio of described graphite and the vitriol oil, concentrated nitric acid and hydrogen peroxide is respectively 1: 80～1: 100,1: 20～1: 30 and 1: 5～1: 30, and the mass ratio of described graphite and potassium permanganate is 1: 1～1: 10.
In the preparation method of above-mentioned boron doped graphene, the consumption of described potassium permanganate and hydrogen peroxide is directly proportional.
In the preparation method of above-mentioned boron doped graphene, described boron source gas is gaseous state boron trichloride or gaseous ethane boron, and described rare gas element is argon gas.
In the preparation method of above-mentioned boron doped graphene, the flow of described rare gas element and boron source gas is 50～400ml/ minute.
In the preparation method of above-mentioned boron doped graphene, the volume ratio of described rare gas element and boron source gas is 1: 8～8: 1.
In the preparation method of above-mentioned boron doped graphene, the temperature rise rate for preparing described boron doped graphene is 10～20 ℃/minute.
According to a further aspect in the invention, provide a kind of boron doped graphene, described boron doped graphene is prepared by the preparation method of above-mentioned boron doped graphene.
Implement the present invention and can obtain following beneficial effect: (1) is compared with other preparation methods, utilize high temperature hot doping method, at high temperature can directly by graphite oxide and the gas reaction of boron source, prepare the boron doped graphene, processing step is few and simple to operate, simultaneously low for equipment requirements, be conducive to realize large-scale industrial production; (2) graphite oxide is the relatively poor carbon material of order, and the material that this order is lower is more suitable in the doping of carrying out boron, adopts the boron source of gaseous form can make the doping process more even; (3) prepared boron doped graphene is the doping of P-type, does not affect the original conjugated structure of Graphene, and has the conductivity more excellent than Graphene.
Embodiment
The invention provides a kind of preparation method of boron doped graphene, the method be take graphite as raw material, after preparing graphite oxide, adopts high temperature hot doping method further to make required boron doped graphene.In high temperature doping process, layering after graphite oxide expands, oxygen element carries out pyrolysis, and graphene sheet layer is peeled off, and the boron atom in the gas of boron source completes the doping of P-type simultaneously.The carbon-to-oxygen ratio of the graphite oxide that the present invention is prepared is less than 3, and the graphite oxide of this type presents a kind of structure lower than the Graphene degree of order.And, for boron doping carbon material, the relative order of carbon material is lower, more easily adulterated.Directly adopt the boron source of gaseous form to make the high temperature doping more easily carry out, and can improve uniform doping.This preparation method is simple to operate, be convenient to realize, raw materials used be easy to get and cost low, prepared boron doped graphene has excellent conductive performance.Below by specific embodiment, the concrete technology flow process that adopts the standby boron doped graphene of high temperature hot doping legal system is described in the present invention.
Embodiment 1:
The graphite that the purity of take is 99.5% is raw material, taking 1g graphite adds in the mixing solutions be comprised of the 92ml vitriol oil (massfraction is 98%) and 24ml concentrated nitric acid (massfraction is 65%), mixing solutions is placed in to frozen water and mixes bath environment stirring 20 minutes, add again 3g potassium permanganate in mixing solutions, stir and within 1 hour, make the preliminary oxidation of graphite, then mixing solutions is heated to 85 ℃, and the insulation processing makes the further oxidation of graphite in 30 minutes, add subsequently the 92ml deionized water, continuation keeps 30 minutes at the temperature of 85 ℃, finally in mixing solutions, add 8ml hydrogen peroxide (massfraction is 30%) to remove potassium permanganate, suction filtration is also washed the gained solid product with 100ml dilute hydrochloric acid and 150ml deionized water, wash altogether three times, then solid product is placed in to 60 ℃ of vacuum drying ovens and makes graphite oxide after dry 12 hours, the graphite oxide made is placed in to the mixed gas atmosphere that flow velocity is argon gas and the boron trichloride of 200ml/min, temperature rise rate with 15 ℃/min is warming up to 900 ℃ by the mixed gas atmosphere, insulation is processed after 2 hours and is made products therefrom be down to room temperature under the argon atmosphere of 200ml/min, obtains the boron doped graphene.
The content of each principal element of boron doped graphene in table 1 embodiment 1
| Test specimens | Carbon (%) | Boron (%) | Oxygen element (%) |
| The boron doped graphene | 86.7 | 3.2 | 10.1 |
Table 1 is tested the content of each principal element obtained for the boron doped graphene prepared in embodiment 1 by XPS.In table, data are known, and the boron-containing quantity of preparation-obtained boron doped graphene is 3.2%, oxygen level is 10.1%.
Embodiment 2:
The graphite that the purity of take is 99.5% is raw material, taking 1g graphite adds in the mixing solutions be comprised of the 92ml vitriol oil (massfraction is 98%) and 20ml concentrated nitric acid (massfraction is 65%), mixing solutions is placed in to frozen water and mixes bath environment stirring 20 minutes, add again 4g potassium permanganate in mixing solutions, stir and within 1 hour, make the preliminary oxidation of graphite, then mixing solutions is heated to 95 ℃, and the insulation processing makes the further oxidation of graphite in 30 minutes, add subsequently the 92ml deionized water, continuation keeps 30 minutes at the temperature of 95 ℃, finally in mixing solutions, add 8ml hydrogen peroxide (massfraction is 30%) to remove potassium permanganate, suction filtration is also washed the gained solid product with 100ml dilute hydrochloric acid and 150ml deionized water, wash altogether three times, then solid product is placed in to 60 ℃ of vacuum drying ovens and makes graphite oxide after dry 12 hours, the graphite oxide made is placed in to the mixed gas atmosphere that flow velocity is respectively argon gas and the ethane boron of 200ml/min and 300ml/min, temperature rise rate with 20 ℃/min is warming up to 1000 ℃ by the mixed gas atmosphere, insulation is processed after 2 hours and is made products therefrom be down to room temperature under the argon atmosphere of 200ml/min, obtains the boron doped graphene.
Embodiment 3:
The graphite that the purity of take is 99.5% is raw material, taking 2g graphite adds in the mixing solutions be comprised of the 160ml vitriol oil (massfraction is 98%) and 60ml concentrated nitric acid (massfraction is 65%), mixing solutions is placed in to frozen water and mixes bath environment stirring 20 minutes, add again 2g potassium permanganate in mixing solutions, stir and within 1 hour, make the preliminary oxidation of graphite, then mixing solutions is heated to 80 ℃, and the insulation processing makes the further oxidation of graphite in 30 minutes, add subsequently the 92ml deionized water, continuation keeps 30 minutes at the temperature of 80 ℃, finally in mixing solutions, add 10ml hydrogen peroxide (massfraction is 30%) to remove potassium permanganate, suction filtration is also washed the gained solid product with 100ml dilute hydrochloric acid and 150ml deionized water, wash altogether three times, then solid product is placed in to 60 ℃ of vacuum drying ovens and makes graphite oxide after dry 12 hours, the graphite oxide made is placed in to the mixed gas atmosphere that flow velocity is respectively argon gas and the boron trichloride of 400ml/min and 50ml/min, temperature rise rate with 20 ℃/min is warming up to 1100 ℃ by the mixed gas atmosphere, insulation is processed after 0.5 hour and is made products therefrom be down to room temperature under the argon atmosphere of 400ml/min, obtains the boron doped graphene.
Embodiment 4:
The graphite that the purity of take is 99.5% is raw material, taking 1g graphite adds in the mixing solutions be comprised of the 100ml vitriol oil (massfraction is 98%) and 25ml concentrated nitric acid (massfraction is 65%), mixing solutions is placed in to frozen water and mixes bath environment stirring 20 minutes, add again 10g potassium permanganate in mixing solutions, stir and within 1 hour, make the preliminary oxidation of graphite, then mixing solutions is heated to 90 ℃, and the insulation processing makes the further oxidation of graphite in 30 minutes, add subsequently the 92ml deionized water, continuation keeps 30 minutes at the temperature of 85 ℃, finally in mixing solutions, add 30ml hydrogen peroxide (massfraction is 30%) to remove potassium permanganate, suction filtration is also washed the gained solid product with 100ml dilute hydrochloric acid and 150ml deionized water, wash altogether three times, then solid product is placed in to 60 ℃ of vacuum drying ovens and makes graphite oxide after dry 12 hours, the graphite oxide made is placed in to the mixed gas atmosphere that flow velocity is respectively argon gas and the ethane boron of 50ml/min and 400ml/min, temperature rise rate with 10 ℃/min is warming up to 800 ℃ by the mixed gas atmosphere, insulation is processed after 2 hours and is made products therefrom be down to room temperature under the argon atmosphere of 200ml/min, obtains the boron doped graphene.
Embodiment 5:
The graphite that the purity of take is 99.5% is raw material, taking 1g graphite adds in the mixing solutions be comprised of the 95ml vitriol oil (massfraction is 98%) and 20ml concentrated nitric acid (massfraction is 65%), mixing solutions is placed in to frozen water and mixes bath environment stirring 20 minutes, add again 5g potassium permanganate in mixing solutions, stir and within 1 hour, make the preliminary oxidation of graphite, then mixing solutions is heated to 70 ℃, and the insulation processing makes the further oxidation of graphite in 30 minutes, add subsequently the 92ml deionized water, continuation keeps 30 minutes at the temperature of 70 ℃, finally in mixing solutions, add 15ml hydrogen peroxide (massfraction is 30%) to remove potassium permanganate, suction filtration is also washed the gained solid product with 100ml dilute hydrochloric acid and 150ml deionized water, wash altogether three times, then solid product is placed in to 60 ℃ of vacuum drying ovens and makes graphite oxide after dry 12 hours, the graphite oxide made is placed in to the mixed gas atmosphere that flow velocity is respectively argon gas and the boron trichloride of 200ml/min and 100ml/min, temperature rise rate with 15 ℃/min is warming up to 900 ℃ by the mixed gas atmosphere, insulation is processed after 1 hour and is made products therefrom be down to room temperature under the argon atmosphere of 200ml/min, obtains the boron doped graphene.
Claims (10)
1. the preparation method of a boron doped graphene, is characterized in that, adopts the standby described boron doped graphene of high temperature hot doping legal system, said method comprising the steps of:
S1: prepare graphite oxide: take graphite as raw material, make graphite oxide after oxidation; And
S2: prepare described boron doped graphene: the mixed gas atmosphere that described graphite oxide is placed in to rare gas element and boron source gas formation, being warming up to 800 ~ 1100 ℃ also is incubated and processes 0.5 ~ 2 hour, products therefrom is cooled to room temperature, obtains described boron doped graphene.
2. the preparation method of boron doped graphene according to claim 1, is characterized in that, in described step S1, the purity of described graphite is 99.5%.
3. the preparation method of boron doped graphene according to claim 1 and 2, it is characterized in that, described step S1 comprises: load weighted graphite is added in the mixing solutions of the vitriol oil and concentrated nitric acid, mix in bath and stir at frozen water, in mixing solutions, add again potassium permanganate to make the preliminary oxidation of graphite, then mixing solutions is heated to 70 ~ 95 ℃, insulation is processed and is made the further oxidation of graphite, in mixing solutions, add again hydrogen peroxide to remove potassium permanganate, suction filtration also carries out repetitive scrubbing with dilute hydrochloric acid and deionized water to products therefrom, make described graphite oxide after drying.
4. the preparation method of boron doped graphene according to claim 3, it is characterized in that, the mass volume ratio of described graphite and the vitriol oil, concentrated nitric acid and hydrogen peroxide is respectively 1:80 ~ 1:100,1:20 ~ 1:30 and 1:5 ~ 1:30, and the mass ratio of described graphite and potassium permanganate is 1:1 ~ 1:10.
5. the preparation method of boron doped graphene according to claim 4, is characterized in that, the consumption of described potassium permanganate and hydrogen peroxide is directly proportional.
6. the preparation method of boron doped graphene according to claim 1, is characterized in that, described boron source gas is gaseous state boron trichloride or gaseous ethane boron, and described rare gas element is argon gas.
7. according to the preparation method of the described boron doped graphene of claim 1 or 6, it is characterized in that, the flow of described rare gas element and boron source gas is 50 ~ 400ml/ minute.
8. the preparation method of boron doped graphene according to claim 7, is characterized in that, the volume ratio of described rare gas element and boron source gas is 1:8 ~ 8:1.
9. the preparation method of boron doped graphene according to claim 1, is characterized in that, the temperature rise rate for preparing described boron doped graphene is 10 ~ 20 ℃/minute.
10. a boron doped graphene, is characterized in that, the preparation method of described boron doped graphene any one claim in claim 1-9 prepares.
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| CN105016328A (en) * | 2014-04-25 | 2015-11-04 | 中国科学院物理研究所 | Method for growing P-type graphene on silicon carbide substrate |
| CN105047925A (en) * | 2015-06-15 | 2015-11-11 | 西北工业大学 | Preparation method for negative electrode material of modified graphite lithium ion battery with high capacity and long service life |
| CN106638107A (en) * | 2016-12-05 | 2017-05-10 | 安徽索亚装饰材料有限公司 | Preparation method of ordorless environment-friendly fiber wallpaper |
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Cited By (6)
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| CN104299798A (en) * | 2014-03-19 | 2015-01-21 | 洛阳力容新能源科技有限公司 | Boron-doped modified graphene material, preparation method and application |
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| CN105047925A (en) * | 2015-06-15 | 2015-11-11 | 西北工业大学 | Preparation method for negative electrode material of modified graphite lithium ion battery with high capacity and long service life |
| CN106638107A (en) * | 2016-12-05 | 2017-05-10 | 安徽索亚装饰材料有限公司 | Preparation method of ordorless environment-friendly fiber wallpaper |
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Application publication date: 20131218 |