CN103359708B - The preparation method of nitrogen-doped graphene - Google Patents
The preparation method of nitrogen-doped graphene Download PDFInfo
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Abstract
A preparation method for nitrogen-doped graphene, comprises the steps: graphite oxide to be scattered in deionized water, carries out supersound process, then suction filtration, dries, obtains graphene oxide; By described graphene oxide and Pluronic? F-127 adds in deionized water successively, stirs 2 ~ 4 hours, does solvent flashing, obtain graphene oxide/Pluronic? F-127 mixture; By described graphene oxide/Pluronic? under F-127 mixture is placed in the mixed gas atmosphere of rare gas element and ammonia, 800 ~ 1000 DEG C are heated to the temperature rise rate of 5 ~ 20 DEG C/min, be incubated 30 ~ 120 minutes, be cooled to room temperature, obtain nitrogen-doped graphene.Does above-mentioned preparation method utilize heat of oxidation reduction method, by introducing Pluronic in the process of preparation? F-127 and introduce nitrogenous source in thermal reduction process, can prepare the nitrogen-doped graphene material that particle diameter is less.
Description
[technical field]
The present invention relates to a kind of preparation method of nitrogen-doped graphene.
[background technology]
Graphene due to advantages such as the conductivity of its excellence, high specific surface area, good mechanical property and snappinesies, has all been with a wide range of applications in a lot of industry since coming out from 2004.The researcher of current industry-by-industry all in the modification that the application characteristic according to this area is carried out to a certain degree to Graphene, thus makes Graphene be utilized by the industry, promotes the industry and advances.Graphene is used for the emphasis that energy storage field is development at present, as Graphene serves as ultracapacitor and lithium ion battery electrode material.From microcosmic angle, Graphene is made up of a lot of banded graphene film, and from macroscopic perspective, Graphene has film and particle two kinds, and corpuscular Graphene serves as electrode materials and has good commercial applications prospect, it is also the emphasis of research at present.The particle size of the graphene powder usually prepared with oxide-reduction method is all at about 10 μm, if be used as electrode materials with the graphene powder of this size, because electrolyte ion is longer in the distance of intra-particle diffusion, and rate of diffusion is slower, therefore be unfavorable for obtaining high power density, thus the development of restriction Graphene in energy storage field.
[summary of the invention]
Based on this, be necessary to provide the preparation method of the nitrogen-doped graphene that a kind of particle diameter is less.
A preparation method for nitrogen-doped graphene, comprises the steps:
Graphite oxide is scattered in deionized water, carries out supersound process, then suction filtration, dry, obtain graphene oxide;
Described graphene oxide and PluronicF-127 are added successively in deionized water, stir 2-4 hour, solvent flashing, obtains graphene oxide/PluronicF-127 mixture;
Under described graphene oxide/PluronicF-127 mixture being placed in the mixed gas atmosphere of rare gas element and ammonia, be heated to 800-1000 DEG C with the temperature rise rate of 5-20 DEG C/min, insulation 30-120 minute, is cooled to room temperature, obtains nitrogen-doped graphene.
In one embodiment, described graphite oxide is adopted and is obtained with the following method:
Graphite is added in the mixing solutions of the vitriol oil and concentrated nitric acid, stir in frozen water mixing bath, in mixing solutions, add potassium permanganate more afterwards, graphite is oxidized, then mixing solutions is heated to 70 ~ 95 DEG C of insulations, graphite is oxidized further, finally add hydrogen peroxide removing potassium permanganate, suction filtration, carries out repetitive scrubbing with dilute hydrochloric acid and deionized water to solids, drying, obtains graphite oxide.
In one embodiment, the volume ratio of the described vitriol oil and concentrated nitric acid is 90 ~ 95: 20 ~ 30; Described graphite and the mass ratio of potassium permanganate are 1: 3 ~ 10.
In one embodiment, the mass ratio of described graphite oxide and described PluronicF-127 is 1: 1 ~ 4.
In one embodiment, the molecular weight of described PluronicF-127 is 12.5K.
In one embodiment, described graphite to be purity be 99.5% graphite.
In one embodiment, the ultrasonic power of described supersound process is 500 ~ 800W, and the time is 1 ~ 2 hour.
In one embodiment, the flow of described rare gas element and ammonia is 150 ~ 400ml/ minute.
In one embodiment, described rare gas element is argon gas.
In one embodiment, add in the step in ether solvent successively by described graphene oxide and PluronicF-127, every gram of graphene oxide joins in the ether solvent of 1.5 ~ 2L.
Above-mentioned preparation method utilizes heat of oxidation reduction method, by introducing PluronicF-127 and introduce nitrogenous source in thermal reduction process in the process of preparation, can prepare the nitrogen-doped graphene material that particle diameter is less.
[accompanying drawing explanation]
Fig. 1 is preparation method's schema of the nitrogen-doped graphene of an embodiment;
Fig. 2 is that nitrogen-doped graphene prepared by embodiment 1 utilizes dynamic laser light scattering instrument to test the grain size distribution drawn.
[embodiment]
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, are described in detail the specific embodiment of the present invention below in conjunction with accompanying drawing.Set forth a lot of detail in the following description so that fully understand the present invention.But the present invention can be much different from alternate manner described here to implement, those skilled in the art can when without prejudice to doing similar improvement when intension of the present invention, therefore the present invention is by the restriction of following public concrete enforcement.
Refer to Fig. 1, the preparation method of the nitrogen-doped graphene of an embodiment comprises the steps.
Step S101 take graphite as raw material, preferably, is raw material, prepares graphite oxide with the graphite that purity is 99.5%.
Graphite is added in the mixing solutions of the vitriol oil and concentrated nitric acid, stir in frozen water mixing bath, in mixing solutions, add potassium permanganate more afterwards, graphite is oxidized, then mixing solutions is heated to 70 ~ 95 DEG C of insulations, graphite is oxidized further, finally add hydrogen peroxide removing potassium permanganate, suction filtration, carries out repetitive scrubbing with dilute hydrochloric acid and deionized water to solids, drying, obtains graphite oxide.
Step S102, is scattered in graphite oxide in deionized water, carries out supersound process, then suction filtration, dries, obtains graphene oxide.
Preferably, graphite oxide can be added with deionized water, form the mixing solutions that concentration is about 1mg/ml, then supersound process is carried out to this mixing solutions.Ultrasonic power is preferably 500 ~ 800W.Ultrasonic stripping, after 1 ~ 2 hour, carries out suction filtration to mixture, and the vacuum drying oven be then placed in by solids at 60 DEG C toasts 12 hours, obtains graphene oxide.
Step S103, adds in ether solvent successively by graphene oxide and PluronicF-127, stirs 2 ~ 4 hours, solvent flashing, obtains graphene oxide/PluronicF-127 mixture.
Preferably, can according to 1g: (1 ~ 4g): the ratio of (1.5 ~ 2L), graphene oxide and PluronicF-127 are joined in ether solvent successively, stir 2 hours, then mixing solutions is placed in stink cupboard, after ether volatilization, obtains the mixture be made up of graphene oxide and PluronicF-127.
PluronicF-127 is the water miscible polyoxyethylene-poly-oxypropylene polyoxyethylene of one (PEO-PPO-PEO) triblock copolymer that BASF AG produces, and its molecular weight is generally 9840 ~ 14600, is preferably 12500.
Ether is selected to be that its solvability is in organic solvent better than the solvability in inorganic solvent (such as water) because PluronicF-127 is organic polymer as solvent.
Step S104, under graphene oxide/PluronicF-127 mixture being placed in the mixed gas atmosphere of rare gas element and ammonia, be heated to 800 ~ 1000 DEG C with the temperature rise rate of 5 ~ 20 DEG C/min, be incubated 30 ~ 120 minutes, be cooled to room temperature, obtain nitrogen-doped graphene.
Preferably, graphene oxide/PluronicF-127 mixture to be placed in flow be the argon gas of 150 ~ 400ml/ minute and flow is under the mixed gas atmosphere of the ammonia of 150 ~ 400ml/ minute, with the temperature rise rate of 10 DEG C/min, the envrionment temperature of graphene oxide/PluronicF-127 mixture is risen to 800 DEG C from room temperature, and keep 30min, make PluronicF-127 pyrolysis, finally under the atmosphere of argon gas (flow is 200ml/ minute), be naturally down to room temperature, obtain nitrogen-doped graphene.Be appreciated that described rare gas element also can be helium, neon, xenon etc.
During heating, heat of oxidation reduction reaction occurs, and ammonia can react with the oxygen-containing functional group on graphene oxide, and temperature continues to rise, and due to the instability of bond energy, the structure on Graphene can be reset, and makes atom N move to basal plane or the edge of Graphene.PluronicF127 is a kind of both sexes molecules surfactant, be added in ether solvent with graphene oxide simultaneously, because graphene oxide is wetting ability, and ether is hydrophobicity, therefore PluronicF127 can be gathered in surface of graphene oxide, graphene oxide is in a small amount made to form a particle, and PluronicF127 is macromole, make can not to occur between particle and particle also molten, and the amount of control PluronicF127 can control the size of particle, the amount of PluronicF127 is more, the quantity of each particle internal oxidition graphene sheet layer is fewer, make the particle diameter of particle less.
The advantage of aforesaid method is: 1, prepared nitrogen-doped graphene material has less particle diameter, can reach micro/nano level; 2, by changing experiment parameter to regulate and control the specific surface area of nitrogen-doped graphene material within the specific limits; 3, mix nitrogen in single-layer graphene, do not affect its conjugated structure, there is excellent conductivity equally; 4, preparation method adopts heat of oxidation reduction method, and equipment, technique are simple, and convenient operation, easily realizes large-scale industrial production.
Followingly to be described further in conjunction with specific embodiments.
Embodiment 1
Step (1), the graphite providing purity to be 99.5%.
Step (2), be that the graphite of 99.5% is for raw material with (1) moderate purity, take step (1) moderate purity be 99.5% graphite 1g add in the mixing solutions be made up of the 92ml vitriol oil (massfraction is 98%) and 24ml concentrated nitric acid (massfraction is 65%), stirring is carried out 20 minutes under mixture being placed in frozen water mixing bath environment, 10g potassium permanganate is added at leisure again in mixture, stir 1 hour, then mixture be heated to 85 DEG C and keep 30 minutes, add 92ml deionized water afterwards to continue to keep 30 minutes at 85 DEG C, finally add 10ml superoxol (massfraction 30%), stir 10 minutes, suction filtration is carried out to mixture, with 100ml dilute hydrochloric acid and 150ml deionized water, solids is washed respectively successively again, wash three times altogether, last solid matter is dry in 60 DEG C of vacuum drying ovens obtains graphite oxide in 12 hours.
Step (3), the graphite oxide of preparation in (2) is added in deionized water, the concentration of graphite oxide in water is 1mg/ml, carry out ultrasonic to the mixture of graphite oxide and water, ultrasonic power is 500W, after 1 hour, suction filtration is carried out to mixture, vacuum drying oven solid matter being placed in 60 DEG C dries 12 hours, obtains graphene oxide.
Step (4), the graphene oxide obtained in (3) and F127 are added (graphene oxide: F127: ether=1g: 4g: 2L) in ether solvent successively, stir 2 hours, mixing solutions is placed in stink cupboard, after solvent evaporates, obtains graphene oxide/F127 mixture.
Step (5), the graphene oxide obtained in (4)/F127 mixture is placed in ammonia (flow is 200ml/min)/argon gas (flow is 200ml/min) atmosphere under, with the temperature rise rate of 10 DEG C/min, the envrionment temperature of graphene oxide/F127 mixture is risen to 800 DEG C from room temperature, and keep 30min, finally under argon gas (flow is 200ml/min) mixed atmosphere, temperature is down to room temperature naturally, obtains nitrogen-doped graphene.
The grain size distribution that the nitrogen-doped graphene particle dynamic laser light scattering instrument of Fig. 1 prepared by the present embodiment tests out, the particle diameter of the nitrogen-doped graphene particle as known in the figure prepared by the present embodiment is within the scope of micro/nano level.
Embodiment 2
Step (1), the graphite providing purity to be 99.5%.
Step (2), be that the graphite of 99.5% is for raw material with (1) moderate purity, take step (1) moderate purity be 99.5% graphite 1g add in the mixing solutions be made up of the 90ml vitriol oil (massfraction is 98%) and 30ml concentrated nitric acid (massfraction is 65%), stirring is carried out 20 minutes under mixture being placed in frozen water mixing bath environment, 8g potassium permanganate is added at leisure again in mixture, stir 1 hour, then mixture be heated to 75 DEG C and keep 30 minutes, add 92ml deionized water afterwards to continue to keep 30 minutes at 85 DEG C, finally add 10ml superoxol (massfraction 30%), stir 10 minutes, suction filtration is carried out to mixture, with 100ml dilute hydrochloric acid and 150ml deionized water, solids is washed respectively successively again, wash three times altogether, last solid matter is dry in 60 DEG C of vacuum drying ovens obtains graphite oxide in 12 hours.
Step (3), the graphite oxide of preparation in (2) is added in deionized water, the concentration of graphite oxide in water is 1mg/ml, carry out ultrasonic to the mixture of graphite oxide and water, ultrasonic power is 600W, after 1.5 hours, suction filtration is carried out to mixture, vacuum drying oven solid matter being placed in 60 DEG C dries 12 hours, obtains graphene oxide.
Step (4), the graphene oxide obtained in (3) and F127 are added (graphene oxide: F127: ether=1g: 3g: 1.5L) in ether solvent successively, stir 2 hours, mixing solutions is placed in stink cupboard, after solvent evaporates, obtains graphene oxide/F127 mixture.
Step (5), the graphene oxide obtained in (4)/F127 mixture is placed in ammonia (flow is 150ml/min)/argon gas (flow is 250ml/min) atmosphere under, with the temperature rise rate of 10 DEG C/min, the envrionment temperature of graphene oxide/F127 mixture is risen to 800 DEG C from room temperature, and keep 30min, finally under argon gas (flow is 200ml/min) mixed atmosphere, temperature is down to room temperature naturally, obtains nitrogen-doped graphene.
Embodiment 3
Step (1), the graphite providing purity to be 99.5%.
Step (2), be that the graphite of 99.5% is for raw material with (1) moderate purity, take step (1) moderate purity be 99.5% graphite 1g add in the mixing solutions be made up of the 93ml vitriol oil (massfraction is 98%) and 27ml concentrated nitric acid (massfraction is 65%), stirring is carried out 20 minutes under mixture being placed in frozen water mixing bath environment, 5g potassium permanganate is added at leisure again in mixture, stir 1 hour, then mixture be heated to 75 DEG C and keep 30 minutes, add 92ml deionized water afterwards to continue to keep 30 minutes at 85 DEG C, finally add 10ml superoxol (massfraction 30%), stir 10 minutes, suction filtration is carried out to mixture, with 100ml dilute hydrochloric acid and 150ml deionized water, solids is washed respectively successively again, wash three times altogether, last solid matter is dry in 60 DEG C of vacuum drying ovens obtains graphite oxide in 12 hours.
Step (3), the graphite oxide of preparation in (2) is added in deionized water, the concentration of graphite oxide in water is 1mg/ml, carry out ultrasonic to the mixture of graphite oxide and water, ultrasonic power is 500W, after 2 hours, suction filtration is carried out to mixture, vacuum drying oven solid matter being placed in 60 DEG C dries 12 hours, obtains graphene oxide.
Step (4), the graphene oxide obtained in (3) and F127 are added (graphene oxide: F127: ether=1g: 2g: 1.5L) in ether solvent successively, stir 2 hours, mixing solutions is placed in stink cupboard, after solvent evaporates, obtains graphene oxide/F127 mixture.
Step (5), the graphene oxide obtained in (4)/F127 mixture is placed in ammonia (flow is 300ml/min)/argon gas (flow is 200ml/min) atmosphere under, with the temperature rise rate of 10 DEG C/min, the envrionment temperature of graphene oxide/F127 mixture is risen to 800 DEG C from room temperature, and keep 30min, finally under argon gas (flow is 200ml/min) mixed atmosphere, temperature is down to room temperature naturally, obtains nitrogen-doped graphene.
Embodiment 4
Step (1), the graphite providing purity to be 99.5%.
Step (2), be that the graphite of 99.5% is for raw material with (1) moderate purity, take step (1) moderate purity be 99.5% graphite 1g add in the mixing solutions be made up of the 95ml vitriol oil (massfraction is 98%) and 20ml concentrated nitric acid (massfraction is 65%), stirring is carried out 20 minutes under mixture being placed in frozen water mixing bath environment, 3g potassium permanganate is added at leisure again in mixture, stir 1 hour, then mixture be heated to 75 DEG C and keep 30 minutes, add 92ml deionized water afterwards to continue to keep 30 minutes at 85 DEG C, finally add 10ml superoxol (massfraction 30%), stir 10 minutes, suction filtration is carried out to mixture, with 100ml dilute hydrochloric acid and 150ml deionized water, solids is washed respectively successively again, wash three times altogether, last solid matter is dry in 60 DEG C of vacuum drying ovens obtains graphite oxide in 12 hours.
Step (3), the graphite oxide of preparation in (2) is added in deionized water, the concentration of graphite oxide in water is 1mg/ml, carry out ultrasonic to the mixture of graphite oxide and water, ultrasonic power is 700W, after 2 hours, suction filtration is carried out to mixture, vacuum drying oven solid matter being placed in 60 DEG C dries 12 hours, obtains graphene oxide.
Step (4), the graphene oxide obtained in (3) and F127 are added (graphene oxide: F127: ether=1g: 1g: 1.5L) in ether solvent successively, stir 2 hours, mixing solutions is placed in stink cupboard, after solvent evaporates, obtains graphene oxide/F127 mixture.
Step (5), the graphene oxide obtained in (4)/F127 mixture is placed in ammonia (flow is 300ml/min)/argon gas (flow is 250ml/min) atmosphere under, with the temperature rise rate of 10 DEG C/min, the envrionment temperature of graphene oxide/F127 mixture is risen to 800 DEG C from room temperature, and keep 30min, finally under argon gas (flow is 200ml/min) mixed atmosphere, temperature is down to room temperature naturally, obtains nitrogen-doped graphene.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a preparation method for nitrogen-doped graphene, is characterized in that, comprises the steps:
Graphite oxide is scattered in deionized water, carries out supersound process, then suction filtration, dry, obtain graphene oxide;
Described graphene oxide and PluronicF-127 are added in ether solvent successively, stirs 2 ~ 4 hours, solvent flashing, obtain graphene oxide/PluronicF-127 mixture;
Under described graphene oxide/PluronicF-127 mixture being placed in the mixed gas atmosphere of rare gas element and ammonia, be heated to 800 ~ 1000 DEG C with the temperature rise rate of 5 ~ 20 DEG C/min, be incubated 30 ~ 120 minutes, be cooled to room temperature, obtain nitrogen-doped graphene.
2. the preparation method of nitrogen-doped graphene according to claim 1, it is characterized in that: described graphite oxide is adopted and obtained with the following method: graphite is added in the mixing solutions of the vitriol oil and concentrated nitric acid, stir in frozen water mixing bath, potassium permanganate is added again afterwards in mixing solutions, graphite is oxidized, then mixing solutions is heated to 70 ~ 95 DEG C of insulations, graphite is oxidized further, finally add hydrogen peroxide removing potassium permanganate, suction filtration, with dilute hydrochloric acid and deionized water, repetitive scrubbing is carried out to solids, dry, obtain graphite oxide.
3. the preparation method of nitrogen-doped graphene according to claim 2, is characterized in that: the volume ratio of the described vitriol oil and concentrated nitric acid is 90 ~ 95:20 ~ 30; Described graphite and the mass ratio of potassium permanganate are 1:3 ~ 10.
4. the preparation method of nitrogen-doped graphene according to claim 1, is characterized in that: the mass ratio of described graphite oxide and described PluronicF-127 is 1:1 ~ 4.
5. the preparation method of nitrogen-doped graphene according to claim 1, is characterized in that: the molecular weight of described PluronicF-127 is 12500.
6. the preparation method of nitrogen-doped graphene according to claim 2, is characterized in that: described graphite to be purity be 99.5% graphite.
7. the preparation method of nitrogen-doped graphene according to claim 1, is characterized in that: the ultrasonic power of described supersound process is 500 ~ 800W, and the time is 1 ~ 2 hour.
8. the preparation method of nitrogen-doped graphene according to claim 1, is characterized in that: the flow of described rare gas element and ammonia is 150 ~ 400mL/ minute.
9. the preparation method of nitrogen-doped graphene according to claim 8, is characterized in that: described rare gas element is argon gas.
10. the preparation method of nitrogen-doped graphene according to claim 1, is characterized in that: add in the step in ether solvent successively by described graphene oxide and PluronicF-127, every gram of graphene oxide joins in the ether solvent of 1.5 ~ 2L.
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| CN104347874A (en) * | 2014-09-09 | 2015-02-11 | 上海纳旭实业有限公司 | High uniformly dispersed cobalt disulfide/graphene composite material and preparation method thereof |
| CN106698410B (en) * | 2016-12-05 | 2019-11-26 | 四川大学 | The preparation method of nitrogen atom doping carbon nanomaterial |
| CN108448068A (en) * | 2017-02-16 | 2018-08-24 | 天津大学 | Self-supporting fluorine nitrogen-doped graphene thin-film material and preparation method thereof |
| CN107364845A (en) * | 2017-08-25 | 2017-11-21 | 广西大学 | A kind of method for preparing nitrogen-doped graphene |
| CN107583664A (en) * | 2017-10-13 | 2018-01-16 | 上海交通大学 | A kind of sulphur/nitrogen co-doped graphene and preparation method thereof |
| CN109824042B (en) * | 2017-11-23 | 2022-04-05 | 中国科学院金属研究所 | Method for regulating and controlling electrochemical stripping of graphene |
| CN108380174A (en) * | 2018-02-07 | 2018-08-10 | 同济大学 | Nitrogen-doped graphene material and its preparation method and application |
| CN113172219B (en) * | 2021-03-29 | 2023-03-28 | 西安交通大学 | Preparation method and application of graphene-reinforced AlSi10Mg nanocomposite |
| CN113353917B (en) * | 2021-07-02 | 2022-11-04 | 哈尔滨师范大学 | Controllable preparation method of self-supporting two-dimensional mesoporous nano material |
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