CN103771398A - Boron-doped graphene, and preparation method and application thereof - Google Patents

Boron-doped graphene, and preparation method and application thereof Download PDF

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Publication number
CN103771398A
CN103771398A CN201210412188.1A CN201210412188A CN103771398A CN 103771398 A CN103771398 A CN 103771398A CN 201210412188 A CN201210412188 A CN 201210412188A CN 103771398 A CN103771398 A CN 103771398A
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doped graphene
preparation
boron
graphene
boron doped
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周明杰
钟辉
王要兵
袁新生
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Abstract

The invention relates to boron-doped graphene and a preparation method thereof. The preparation method comprises the following steps: (a) preparing graphene oxide; (b) preparing the boron-doped graphene. The invention further relates to the application of the boron-doped graphene to an electrochemical capacitor or a lithium ion battery as an electrode material. According to the boron-doped graphene, and the preparation method and application thereof, boric acid is used as a boron source, the prepared boron-doped graphene is high in boron content, the boron content can be regulated within a certain range by regulating the content of the boric acid, and boron is uniformly doped; equipment and a process for the adopted high-temperature doping method are simple, the high-temperature doping method is convenient to operate and low in raw material cost, and the boron-doped graphene is easy to realize industrial production.

Description

Boron doped graphene and preparation method thereof and application
Technical field
The present invention relates to electrochemical field, relate in particular to a kind of boron doped graphene and preparation method thereof.The invention still further relates to the application in electrochemical capacitor or lithium ion battery as electrode materials of this boron doped graphene.
Background technology
Nineteen nineties, carbon material has promoted greatly developing of ultracapacitor, lithium ion battery as the use of energy storage material.And Graphene is as a kind of new carbon, since within 2004, being found, due to its two-dimentional unimolecular layer structure and excellent physical properties, as high theoretical specific surface area, excellent physical strength, good snappiness and high specific conductivity etc., will bring change to the material in the fields such as the energy.And the very easy derivatize of Graphene, its derivative is also subject to investigator's extensive concern, and Graphene derivative mainly contains nitrogen-doped graphene and boron doped graphene at present.Wherein boron doped graphene, due to the outer few electronics of boron atom ratio carbon atom, is the doping of P-type, compare Graphene and have better energy-storage property, and the boron content of boron doped graphene is higher, and energy-storage property is better.At present, easily realizing heavy industrialization, to prepare the method for boron doped graphene be high temperature hot doping method, and two greatest problem that boron doped graphene prepared by this method faces to be at present boron content lower and boron doping is inhomogeneous.
Summary of the invention
The object of the invention is to solve the problem and shortage that above-mentioned prior art exists, a kind of boron doped graphene and preparation method thereof and the application in electrochemical capacitor or lithium ion battery as electrode materials of this boron doped graphene are provided.
The technical scheme that the present invention is directed to above-mentioned technical problem and propose is: a kind of preparation method of boron doped graphene, comprises the steps.
(a) prepare graphene oxide: graphite oxide is dispersed in deionized water, and ultrasonic rear filtration, obtains graphene oxide after oven dry filtrate.
(b) prepare boron doped graphene: graphene oxide prepared in step (a) is mixed 1 ~ 5:2 ~ 10 in mass ratio with boric acid, be placed under atmosphere of inert gases, mixture temperature around risen to 900~1100 ° of C heating reductions and be down to again room temperature and obtain boron doped graphene.
(c) purifying of boron doped graphene: the sodium hydroxide solution that boron doped graphene prepared in step (b) is placed in to 100ml 3mol/L, stir and filter to obtain solid product after 2 hours, use again the solid product after deionized water washing and filtering, until pH value is neutral, then solid product is placed in to dry 12 hours of the vacuum drying oven of 60 ° of C.
In described step (a), it is 0.5~2mg/ml that described graphite oxide is dispersed in the solubility obtaining in deionized water; The described ultrasonic time is 1~2 hour; Described oven dry is to carry out in the vacuum drying oven of 40 ° of C of temperature, and drying time is 12 hours.
In described step (b), after described graphene oxide and boric acid are even as solvent with dehydrated alcohol, stir until absolute ethanol volatilizes is complete; The flow velocity of described rare gas element is 200~400ml/ minute, and temperature rise rate is 5 ° of C/ minute; Described graphene oxide needs to keep 2 ~ 4 hours after being warmed up to 900~1300 ° of C.
In described step (a), described graphite oxide is adopted with the following method and is made: the graphite of purity 99.5% is joined in the mixing solutions that massfraction is 98% the vitriol oil and the massfraction concentrated nitric acid composition that is 65%, stir in backward described mixing solutions and add potassium permanganate heated oxide, add again the superoxol of massfraction 30% to stir to remove potassium permanganate, then described mixing solutions is carried out to suction filtration and obtain suction filtration thing, more obtain described graphite oxide after described suction filtration thing washing being dried with dilute hydrochloric acid and deionized water successively.The mass volume ratio of described graphite, the described vitriol oil, described concentrated nitric acid, described potassium permanganate and described hydrogen peroxide is 1-5g:90-200ml:20-100ml:6-20g:9-30ml.In the described vacuum drying oven being dried under 60 ° of C, carry out, the described dry time is 12 hours.
The present invention also comprises the application as electrode materials in electrochemical capacitor or lithium ion battery of the boron doped graphene that makes by above-mentioned preparation method and this boron doped graphene.
The method advantage that the present invention prepares boron doped graphene is: utilize boric acid as boron source, prepared boron doped graphene boron content is higher, and can regulate within the specific limits the content of boron by the content of adjusting boric acid, and boron doping is more even; The high temperature doping method equipment, the technique that use are simple, convenient operation, and the cheap cost of raw material is low, easily realizes large-scale industrial production.
Embodiment
Below in conjunction with embodiment, the present invention is given to elaboration further.Following examples are for the present invention is described, to instruct those skilled in the art to realize the present invention, the present embodiment does not limit the present invention in any way.
the preparation of boron doped graphene:concrete preparation technology's flow process of boron doped graphene of the present invention is as follows: the purifying of graphite → graphite oxide → graphene oxide → boron doped graphene → boron doped graphene.
Concrete preparation process is roughly divided into following steps.
(1) prepare graphite oxide: the graphite of purity 99.5% is joined in the mixing solutions that massfraction is 98% the vitriol oil and the massfraction concentrated nitric acid composition that is 65%, stir in backward described mixing solutions and add potassium permanganate heated oxide, add again the superoxol of massfraction 30% to stir to remove potassium permanganate, then mixing solutions is carried out to suction filtration and obtain suction filtration thing, after suction filtration thing being washed, is dried with dilute hydrochloric acid and deionized water successively again, obtain graphite oxide, graphite oxide is dry in vacuum drying oven under 60 ° of C, and be 12 hours time of drying.
Wherein, the mass volume ratio of graphite, the vitriol oil, concentrated nitric acid, potassium permanganate and hydrogen peroxide is: 1-5g:90-200ml:20-100ml:6-20g:9-30ml.
(2) prepare graphene oxide: prepared graphite oxide in step (1) is dispersed in deionized water, the graphite oxide solubility obtaining is 0.5~2mg/ml, after ultrasonic 1~2 hour, filter, in the vacuum drying oven at 40 ° of C temperature, dry and after filtrate, obtain graphene oxide in 12 hours.
(3) preparing boron doped graphene: by graphene oxide prepared in step (2) and boric acid (1-5) g:(3-10 in mass ratio) g mixes, be placed under atmosphere of inert gases, mixture temperature around risen to 900~1300 ° of C heating reductions and be down to again room temperature and obtain boron doped graphene.
(4) purifying of boron doped graphene: the sodium hydroxide solution that boron doped graphene prepared in step (3) is placed in to 100ml 3mol/L, stir and filter to obtain solid product after 2 hours, use again the solid product after deionized water washing and filtering, until pH value is neutral, then solid product is placed in to dry 12 hours of the vacuum drying oven of 60 ° of C.
Be specifically described with 1~4 couple of boron doped graphene preparation method of the present invention of embodiment below.
It is as follows that the present invention prepares the technical process of boron doped graphene: the purifying of graphite → graphite oxide → graphene oxide → boron doped graphene → boron doped graphene.
embodiment 1:(1) prepare graphite oxide: take purity and be 99.5% graphite 1g and add in the mixing solutions being formed by the 90ml vitriol oil (massfraction is 98%) and 25ml concentrated nitric acid (massfraction is 65%), mixture is placed under frozen water mixing bath environment and is stirred 20 minutes, in mixture, add 8g potassium permanganate at leisure again, stir 1 hour, then mixture is heated to 85 ° of C and keeps 30 minutes, add afterwards 92ml deionized water to continue to keep 30 minutes under 85 ° of C, finally add 9ml superoxol (massfraction 30%), stir 10 minutes, mixture is carried out to suction filtration, with 100ml dilute hydrochloric acid and 150ml deionized water, solids is washed respectively successively again, wash altogether three times, last solid matter is the dry graphite oxide that obtains for 12 hours in 60 ° of C vacuum drying ovens.
(2) prepare graphene oxide: the graphite oxide of preparation in step (1) is added in deionized water, the solubility of graphite oxide in water is 1mg/ml, to mixture ultrasonic 1 hour, filters, the vacuum drying oven that solid product is placed in to 40 ° of C is dried 12 hours, obtains graphene oxide.
(3) prepare boron doped graphene: get the graphene oxide 1g obtaining in step (2) and mix with 3g boric acid, and add the dehydrated alcohol of 10ml with dissolved oxygen Graphene and boric acid, stir until absolute ethanol volatilizes is complete, then mixture is placed under argon gas (flow velocity: 400ml/min) atmosphere, with 5 ° of C/min temperature rise rates, mixture temperature is around risen to 1100 ° of C, and keep 2 hours, finally drop to room temperature in argon gas (flow velocity: 400ml/min) atmosphere and obtain boron doped graphene.
(4) purifying of boron doped graphene: the sodium hydroxide solution that the boron doped graphene obtaining in step (3) is placed in to 100ml, 3mol/L, stir and filter to obtain solid product after 2 hours, use again the solid product after deionized water washing and filtering, until pH value is neutral, then solid product is placed in to dry 12 hours of the vacuum drying oven of 60 ° of C.
embodiment 2:(1) prepare graphite oxide: take purity and be 99.5% graphite 2g and add in the mixing solutions being formed by the 95ml vitriol oil (massfraction is 98%) and 20ml concentrated nitric acid (massfraction is 65%), mixture is placed under frozen water mixing bath environment and is stirred 20 minutes, in mixture, add 12g potassium permanganate at leisure again, stir 1 hour, then mixture is heated to 85 ° of C and keeps 30 minutes, add afterwards 92ml deionized water to continue to keep 30 minutes under 85 ° of C, finally add 9ml superoxol (massfraction 30%), stir 10 minutes, mixture is carried out to suction filtration, with 100ml dilute hydrochloric acid and 150ml deionized water, solids is washed respectively successively again, wash altogether three times, last solid matter is the dry graphite oxide that obtains for 12 hours in 60 ° of C vacuum drying ovens.
(2) prepare graphene oxide: the graphite oxide of preparation in step (1) is added in deionized water, the solubility of graphite oxide in water is 0.5mg/ml, to mixture ultrasonic 1 hour, filters, the vacuum drying oven that solid product is placed in to 40 ° of C is dried 12 hours, obtains graphene oxide.
(3) prepare boron doped graphene: get the graphene oxide 2g obtaining in step (2) and mix with 5g boric acid, and add the dehydrated alcohol of 20ml with dissolved oxygen Graphene and boric acid, stir until absolute ethanol volatilizes is complete, then mixture is placed under argon gas (flow velocity: 300ml/min) atmosphere, with 5 ° of C/min temperature rise rates, mixture temperature is around risen to 900 ° of C, and keep 4 hours, finally drop to room temperature in argon gas (flow velocity: 300ml/min) atmosphere and obtain boron doped graphene.
(4) purifying of boron doped graphene: the sodium hydroxide solution that the boron doped graphene obtaining in step (3) is placed in to 100ml, 3mol/L, stir and filter to obtain solid product after 2 hours, use again the solid product after deionized water washing and filtering, until pH value is neutral, then solid product is placed in to dry 12 hours of the vacuum drying oven of 60 ° of C.
embodiment 3:(1) prepare graphite oxide: take purity and be 99.5% graphite 5g and add in the mixing solutions being formed by the 200ml vitriol oil (massfraction is 98%) and 100ml concentrated nitric acid (massfraction is 65%), mixture is placed under frozen water mixing bath environment and is stirred 20 minutes, in mixture, add 20g potassium permanganate at leisure again, stir 1 hour, then mixture is heated to 85 ° of C and keeps 30 minutes, add afterwards 250ml deionized water to continue to keep 30 minutes under 85 ° of C, finally add 30ml superoxol (massfraction 30%), stir 10 minutes, mixture is carried out to suction filtration, with 300ml dilute hydrochloric acid and 500ml deionized water, solids is washed respectively successively again, wash altogether three times, last solid matter is the dry graphite oxide that obtains for 12 hours in 60 ° of C vacuum drying ovens.
(2) prepare graphene oxide: the graphite oxide of preparation in step (1) is added in deionized water, the solubility of graphite oxide in water is 2mg/ml, to mixture ultrasonic 2 hours, filters, the vacuum drying oven that solid product is placed in to 40 ° of C is dried 12 hours, obtains graphene oxide.
(3) prepare boron doped graphene: get the graphene oxide 3g obtaining in step (2) and mix with 10g boric acid, and add the dehydrated alcohol of 30ml with dissolved oxygen Graphene and boric acid, stir until absolute ethanol volatilizes is complete, then mixture is placed under argon gas (flow velocity: 200ml/min) atmosphere, with 5 ° of C/min temperature rise rates, mixture temperature is around risen to 1300 ° of C, and keep 3 hours, finally drop to room temperature in argon gas (flow velocity: 200ml/min) atmosphere and obtain boron doped graphene.
(4) purifying of boron doped graphene: the sodium hydroxide solution that the boron doped graphene obtaining in step (3) is placed in to 100ml, 3mol/L, stir and filter to obtain solid product after 2 hours, use again the solid product after deionized water washing and filtering, until pH value is neutral, then solid product is placed in to dry 12 hours of the vacuum drying oven of 60 ° of C.
embodiment 4:(1) prepare graphite oxide: take purity and be 99.5% graphite 1g and add in the mixing solutions being formed by the 95ml vitriol oil (massfraction is 98%) and 25ml concentrated nitric acid (massfraction is 65%), mixture is placed under frozen water mixing bath environment and is stirred 20 minutes, in mixture, add 6g potassium permanganate at leisure again, stir 1 hour, then mixture is heated to 85 ° of C and keeps 30 minutes, add afterwards 92ml deionized water to continue to keep 30 minutes under 85 ° of C, finally add 8ml superoxol (massfraction 30%), stir 10 minutes, mixture is carried out to suction filtration, with 100ml dilute hydrochloric acid and 150ml deionized water, solids is washed respectively successively again, wash altogether three times, last solid matter is the dry graphite oxide that obtains for 12 hours in 60 ° of C vacuum drying ovens.
(2) prepare graphene oxide: the graphite oxide of preparation in step (1) is added in deionized water, the solubility of graphite oxide in water is 0.8mg/ml, to mixture ultrasonic 2 hours, filters, the vacuum drying oven that solid product is placed in to 40 ° of C is dried 12 hours, obtains graphene oxide.
(3) prepare boron doped graphene: get the graphene oxide 5g obtaining in step (2) and mix with 5g boric acid, and add the dehydrated alcohol of 40ml with dissolved oxygen Graphene and boric acid, stir until absolute ethanol volatilizes is complete, then mixture is placed under argon gas (flow velocity: 400ml/min) atmosphere, with 5 ° of C/min temperature rise rates, mixture temperature is around risen to 1100 ° of C, and keep 2 hours, finally drop to room temperature in argon gas (flow velocity: 400ml/min) atmosphere and obtain boron doped graphene.
(4) purifying of boron doped graphene: the sodium hydroxide solution that the boron doped graphene obtaining in step (3) is placed in to 100ml, 3mol/L, stir and filter to obtain solid product after 2 hours, use again the solid product after deionized water washing and filtering, until pH value is neutral, then solid product is placed in to dry 12 hours of the vacuum drying oven of 60 ° of C.
In the step of each embodiment (3), some row reactions have occurred above, first boric acid itself can change by some row of generation, becomes metaboric acid, finally becomes boron trioxide, and boron trioxide occurs to react as follows with carbon again: xB 2o 3+ (2+3x) C (Graphene) → 2B xc (Graphene)+3x CO.
Following table 1 is embodiment 1-4 key process parameter.
Figure DEST_PATH_IMAGE002AAA
Table 2: the boron doped graphene principal element content that each embodiment is prepared.
Embodiment Carbon (%) Boron (%) Oxygen element (%)
Embodiment 1 81.5 12.4 6.1
Embodiment 2 81.0 11.7 7.3
Embodiment 3 81.6 12.8 5.6
Embodiment 4 83.1 9.1 7.8
Known by upper table, the boron content of the prepared boron doped graphene of the present invention is higher, all, more than 9%, is up to 12.8%.
The present invention utilizes boric acid as boron source, and prepared boron doped graphene boron content is higher, and can regulate within the specific limits the content of boron by the content of adjusting boric acid, and boron doping is more even; The high temperature doping method equipment, the technique that use are simple, convenient operation, and the cheap cost of raw material is low, easily realizes large-scale industrial production.
Foregoing; it is only preferred embodiment of the present invention; not for limiting embodiment of the present invention; those of ordinary skills are according to main design of the present invention and spirit; can carry out very easily corresponding flexible or modification, therefore protection scope of the present invention should be as the criterion with the desired protection domain of claims.

Claims (9)

1. a preparation method for boron doped graphene, is characterized in that, comprises the steps:
(a) prepare graphene oxide: graphite oxide is dispersed in deionized water, and ultrasonic rear filtration, obtains graphene oxide after oven dry filtrate;
(b) prepare boron doped graphene: graphene oxide prepared in step (a) is mixed 1 ~ 5:2 ~ 10 in mass ratio with boric acid, be placed under atmosphere of inert gases, mixture temperature around risen to 900~1300 ° of C heating reductions and be down to again room temperature and obtain boron doped graphene.
2. preparation method according to claim 1, it is characterized in that, described preparation method also comprises the purification step (c) of described boron doped graphene: the sodium hydroxide solution that boron doped graphene prepared in step (b) is placed in to 100ml 3mol/L, stir and filter to obtain solid product after 2 hours, use again the solid product after deionized water washing and filtering, until pH value is neutral, then solid product is placed in to dry 12 hours of the vacuum drying oven of 60 ° of C.
3. preparation method according to claim 1, is characterized in that, in described step (a), it is 0.5~2mg/ml that described graphite oxide is dispersed in the solubility obtaining in deionized water; The described ultrasonic time is 1~2 hour; Described oven dry is to carry out in the vacuum drying oven of 40 ° of C of temperature, and drying time is 12 hours.
4. preparation method according to claim 1, is characterized in that, in described step (b), after described graphene oxide and boric acid are even as solvent with dehydrated alcohol, stirs until absolute ethanol volatilizes is complete; The flow velocity of described rare gas element is 200~400ml/ minute, and temperature rise rate is 5 ° of C/ minute; Described graphene oxide needs to keep 2 ~ 4 hours after being warmed up to 900~1100 ° of C.
5. preparation method according to claim 1, it is characterized in that, in described step (a), described graphite oxide is adopted with the following method and is made: the graphite of purity 99.5% is joined in the mixing solutions that massfraction is 98% the vitriol oil and the massfraction concentrated nitric acid composition that is 65%, stir in backward described mixing solutions and add potassium permanganate heated oxide, add again the superoxol of massfraction 30% to stir to remove potassium permanganate, then described mixing solutions is carried out to suction filtration and obtain suction filtration thing, after described suction filtration thing washing being dried with dilute hydrochloric acid and deionized water successively again, obtain described graphite oxide.
6. preparation method according to claim 5, is characterized in that, the mass volume ratio of described graphite, the described vitriol oil, described concentrated nitric acid, described potassium permanganate and described hydrogen peroxide is 1-5g:90-200ml:20-100ml:6-20g:9-30ml.
7. preparation method according to claim 5, is characterized in that, in the described vacuum drying oven being dried under 60 ° of C, carries out, and the described dry time is 12 hours.
8. the boron doped graphene that the arbitrary described preparation method of claim 1 to 7 makes.
Boron doped graphene claimed in claim 8 in electrochemical capacitor or lithium ion battery as the application of electrode materials.
CN201210412188.1A 2012-10-25 2012-10-25 Boron-doped graphene, and preparation method and application thereof Pending CN103771398A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106365158A (en) * 2016-07-15 2017-02-01 内江师范学院 Preparation method of graphene oxide, and preparation method of boron-doped reduced graphene oxide
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
CN107651662A (en) * 2017-07-23 2018-02-02 北京化工大学 It is a kind of to prepare boron, the method for nitrogen codope charcoal-aero gel
CN110028961A (en) * 2019-03-08 2019-07-19 南昌大学 Boron carbide nanometer sheet/boron doping graphene quantum dot preparation method and its electroreduction ammonia application
JP2020521718A (en) * 2017-05-31 2020-07-27 ハイドロゲン イン モーション インコーポレイテッド (エイチ2エム) Hydrogen storage product and method for producing the same
CN111646459A (en) * 2020-06-12 2020-09-11 北京航空航天大学 Preparation method and application of boron-doped graphene material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
TRAN VAN KHAI ET AL.: ""Comparison study of structural and optical properties of boron-doped and undoped graphene oxide films"", 《CHEMICAL ENGINEERING JOURNAL》 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106365158A (en) * 2016-07-15 2017-02-01 内江师范学院 Preparation method of graphene oxide, and preparation method of boron-doped reduced graphene oxide
JP2020521718A (en) * 2017-05-31 2020-07-27 ハイドロゲン イン モーション インコーポレイテッド (エイチ2エム) Hydrogen storage product and method for producing the same
JP7136889B2 (en) 2017-05-31 2022-09-13 ハイドロゲン イン モーション インコーポレイテッド (エイチ2エム) Hydrogen storage product and method of making same
US11634321B2 (en) 2017-05-31 2023-04-25 Hydrogen In Motion Inc. (H2M) Hydrogen storage product and method for manufacturing same
CN107651662A (en) * 2017-07-23 2018-02-02 北京化工大学 It is a kind of to prepare boron, the method for nitrogen codope charcoal-aero gel
CN107651662B (en) * 2017-07-23 2020-04-17 北京化工大学 Method for preparing boron-nitrogen double-doped carbon aerogel
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
CN110028961A (en) * 2019-03-08 2019-07-19 南昌大学 Boron carbide nanometer sheet/boron doping graphene quantum dot preparation method and its electroreduction ammonia application
CN111646459A (en) * 2020-06-12 2020-09-11 北京航空航天大学 Preparation method and application of boron-doped graphene material

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