CN103359708A - Preparation method of nitrogen-doped graphene - Google Patents
Preparation method of nitrogen-doped graphene Download PDFInfo
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- CN103359708A CN103359708A CN2012100844275A CN201210084427A CN103359708A CN 103359708 A CN103359708 A CN 103359708A CN 2012100844275 A CN2012100844275 A CN 2012100844275A CN 201210084427 A CN201210084427 A CN 201210084427A CN 103359708 A CN103359708 A CN 103359708A
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Abstract
The invention provides a preparation method of nitrogen-doped graphene. The preparation method comprises the following steps of dispersing graphite oxide in deionized water, carrying out ultrasonic processing, and then leaching and drying the product to obtain graphene oxide; adding the graphene oxide and Pluronic F-127 to the deionized water in sequence, stirring the materials for 2-4 hours, and volatilizing a solvent to obtain a graphene oxide/Pluronic F-127 mixture; and putting the graphene oxide/Pluronic F-127 mixture in the atmosphere of a mixture of inert gas and ammonia gas, heating the mixture to 800-1000 DEG C at a heating rate of 5-20 DEG C/min, preserving heat for 30-120 minutes, and cooling the product to the room temperature, thus obtaining the nitrogen-doped graphene. The preparation method has the beneficial effects that an oxidative thermal reaction method is utilized; and the nitrogen-doped graphene material with a smaller grain size can be prepared by introducing the Pluronic F-127 in a preparation process and introducing the nitrogen source in a thermal reduction process.
Description
[technical field]
The present invention relates to a kind of preparation method of nitrogen-doped graphene.
[background technology]
Graphene is since 2004 come out, because the advantages such as its excellent conductivity, high specific surface area, good mechanical property and snappiness all are with a wide range of applications in a lot of industries.At present the researcher of industry-by-industry is all carrying out to a certain degree modification according to the application characteristic of this area to Graphene, thereby Graphene is utilized by the industry, and the promotion industry advances.It is an emphasis that develops at present that Graphene is used for the energy storage field, serves as ultracapacitor and lithium ion battery electrode material such as Graphene.From microcosmic angle, Graphene is comprised of the graphene film of a lot of band shapes, and from macroscopic perspective, Graphene has two kinds of film and particles, and corpuscular Graphene serves as electrode materials and has good commercial applications prospect, also is the present emphasis of research.The particle size of the graphene powder that usually prepares with oxide-reduction method is all about 10 μ m, if the graphene powder with this size is used as electrode materials, because electrolyte ion is longer in the distance of particle internal diffusion, and rate of diffusion is slower, therefore be unfavorable for obtaining high power density, thereby the restriction Graphene is in the development in energy storage field.
[summary of the invention]
Based on this, be necessary to provide the preparation method of the less nitrogen-doped graphene of a kind of particle diameter.
A kind of preparation method of nitrogen-doped graphene comprises the steps:
Graphite oxide is scattered in the deionized water, carries out supersound process, then suction filtration is dried, and obtains graphene oxide;
Described graphene oxide and Pluronic F-127 are added in the deionized water successively, stirred 2-4 hour, solvent flashing obtains graphene oxide/Pluronic F-127 mixture;
Described graphene oxide/Pluronic F-127 mixture is placed under the mixed gas atmosphere of rare gas element and ammonia, be heated to 800-1000 ℃ with 5-20 ℃/minute temperature rise rate, be incubated 30-120 minute, be cooled to room temperature, obtain nitrogen-doped graphene.
In one embodiment, described graphite oxide adopts following method to make:
Graphite is added in the mixing solutions of the vitriol oil and concentrated nitric acid, mix stirring in the bath at frozen water, in mixing solutions, add potassium permanganate more afterwards, graphite is carried out oxidation, then mixing solutions is heated to 70～95 ℃ of insulations, graphite is further carried out oxidation, add at last hydrogen peroxide and remove 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; The mass ratio of described graphite and potassium permanganate is 1: 3～10.
In one embodiment, the mass ratio of described graphite oxide and described Pluronic F-127 is 1: 1～4.
In one embodiment, the molecular weight of described Pluronic F-127 is 12.5K.
In one embodiment, described graphite is that purity is 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, described graphene oxide and Pluronic F-127 are added in the step in the ether solvent successively, every gram graphene oxide joins in the ether solvent of 1.5～2L.
Above-mentioned preparation method utilizes heat of oxidation reduction method, by introducing Pluronic F-127 and introduce nitrogenous source in the process of preparation in the thermal reduction process, can prepare the less nitrogen-doped graphene material of particle diameter.
[description of drawings]
Fig. 1 is preparation method's schema of the nitrogen-doped graphene of an embodiment;
Fig. 2 is the size distribution figure that the nitrogen-doped graphene of embodiment 1 preparation utilizes the test of dynamic laser light scattering apparatus to draw.
[embodiment]
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, below in conjunction with accompanying drawing the specific embodiment of the present invention is described in detail.A lot of details have been set forth in the following description so that fully understand the present invention.But the present invention can implement much to be different from alternate manner described here, and those skilled in the art can be in the situation that do similar improvement without prejudice to intension of the present invention, so the present invention is not subjected to the restriction of following public implementation.
See also Fig. 1, the preparation method of the nitrogen-doped graphene of an embodiment comprises the steps.
Step S101, preferred take graphite as raw material, be that 99.5% graphite is raw material with purity, prepare graphite oxide.
Graphite is added in the mixing solutions of the vitriol oil and concentrated nitric acid, mix stirring in the bath at frozen water, in mixing solutions, add potassium permanganate more afterwards, graphite is carried out oxidation, then mixing solutions is heated to 70～95 ℃ of insulations, graphite is further carried out oxidation, add at last hydrogen peroxide and remove 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 the deionized water, carries out supersound process, and then suction filtration is dried, and obtains graphene oxide.
Preferably, can form the mixing solutions that concentration is about 1mg/ml with in graphite oxide adding and the deionized water, then this mixing solutions be carried out supersound process.Ultrasonic power is preferably 500～800W.Ultrasonic peel off 1～2 hour after, mixture is carried out suction filtration, then solids is placed the vacuum drying oven baking 12 hours under 60 ℃, obtain graphene oxide.
Step S103 adds graphene oxide and Pluronic F-127 in the ether solvent successively, stirs 2～4 hours, and solvent flashing obtains graphene oxide/Pluronic F-127 mixture.
Preferably, can be according to 1g: (1～4g): (1.5～2L) ratio, join successively graphene oxide and PluronicF-127 in the ether solvent, stirred 2 hours, then mixing solutions is placed in the stink cupboard, after the ether volatilization, obtain the mixture that is formed by graphene oxide and Pluronic F-127.
Pluronic F-127 is a kind of water miscible polyoxyethylene-poly-oxypropylene polyoxyethylene (PEO-PPO-PEO) triblock copolymer that BASF AG produces, and its molecular weight is generally 9840～14600, is preferably 12500.
Selecting ether is that its solvability in organic solvent is better than the solvability in inorganic solvent (for example water) because Pluronic F-127 is organic polymer as solvent.
Step S104, graphene oxide/Pluronic F-127 mixture is placed under the mixed gas atmosphere of rare gas element and ammonia, be heated to 800～1000 ℃ with 5～20 ℃/minute temperature rise rates, be incubated 30～120 minutes, be cooled to room temperature, obtain nitrogen-doped graphene.
Preferably, it is under the mixed gas atmosphere of 150～400ml/ minute argon gas and the flow ammonia that is 150～400ml/ minute that graphene oxide/Pluronic F-127 mixture is placed flow, with the temperature rise rate of 10 ℃/min the envrionment temperature of graphene oxide/Pluronic F-127 mixture is risen to 800 ℃ from room temperature, and maintenance 30min, make Pluronic F-127 pyrolysis, under the atmosphere of argon gas (flow is 200ml/ minute), naturally be down to room temperature at last, 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, ammonia can with graphene oxide on oxygen-containing functional group react, temperature continues to rise because bond energy is unstable, the structure on the Graphene can be reset, so that the N atom moves to basal plane or the edge of Graphene.Pluronic F127 is a kind of both sexes molecules surfactant, be added to simultaneously in the ether solvent with graphene oxide, because graphene oxide is wetting ability, and ether is hydrophobicity, therefore Pluronic F127 can be gathered in the graphene oxide surface, so that graphene oxide in a small amount forms a particle, and Pluronic F127 is macromole, so that can not occur also molten between particle and the particle, and the amount that can control Pluronic F127 is controlled the size of particle, the amount of Pluronic F127 is more, and the quantity of graphene oxide lamella is just fewer in each particle, so that the particle diameter of particle is less.
The advantage of aforesaid method is: 1, prepared nitrogen-doped graphene material has less particle diameter, can reach micro/nano level; 2, can be by changing experiment parameter to regulate and control within the specific limits the specific surface area of nitrogen-doped graphene material; 3, mix nitrogen in the single-layer graphene, do not affect its conjugated structure, have equally excellent conductivity; 4, the preparation method adopts heat of oxidation reduction method, and equipment, technique are simple, and convenient operation is easily realized large-scale industrial production.
Followingly be described further in conjunction with specific embodiments.
Embodiment 1
Step (1), purity is provided is 99.5% graphite.
Step (2), take the graphite of (1) moderate purity as 99.5% as raw material, taking by weighing step (1) moderate purity and be 99.5% graphite 1g adds in the mixing solutions that is comprised of the 92ml vitriol oil (massfraction is 98%) and 24ml concentrated nitric acid (massfraction is 65%), placing frozen water to mix under the bath environment in mixture stirred 20 minutes, in mixture, add 10g potassium permanganate at leisure again, stirred 1 hour, then with mixture heating up to 85 ℃ and kept 30 minutes, adding afterwards the 92ml deionized water continued 85 ℃ of lower maintenances 30 minutes, add at last 10ml superoxol (massfraction 30%), stirred 10 minutes, mixture is carried out suction filtration, with 100ml dilute hydrochloric acid and 150ml deionized water solids is washed respectively successively again, wash altogether three times, last solid matter drying in 60 ℃ of vacuum drying ovens obtained graphite oxide in 12 hours.
In step (3), the graphite oxide adding deionized water with preparation in (2), the concentration of graphite oxide in water is 1mg/ml, mixture to graphite oxide and water carries out ultrasonic, ultrasonic power is 500W, after 1 hour mixture is carried out suction filtration, place 60 ℃ vacuum drying oven to dry by the fire 12 hours solid matter, obtain graphene oxide.
Step (4), graphene oxide and the F127 that obtains in (3) added (graphene oxide: F127: ether=1g: 4g: 2L) in the ether solvent successively, stirred 2 hours, mixing solutions is placed stink cupboard, after solvent evaporates, obtain graphene oxide/F127 mixture.
Step (5), the graphene oxide that obtains in (4)/F127 mixture is placed under ammonia (flow is 200ml/min)/argon gas (flow is 200ml/min) atmosphere, with the temperature rise rate of 10 ℃/min the envrionment temperature of graphene oxide/F127 mixture is risen to 800 ℃ from room temperature, and maintenance 30min, temperature is down to room temperature naturally under argon gas (flow is 200ml/min) mixed atmosphere at last, obtains nitrogen-doped graphene.
Fig. 1 is the size distribution figure that the prepared nitrogen-doped graphene particle of the present embodiment tests out with the dynamic laser light scattering apparatus, and the particle diameter of the prepared nitrogen-doped graphene particle of the present embodiment is in the micro/nano level scope as known in the figure.
Embodiment 2
Step (1), purity is provided is 99.5% graphite.
Step (2), take the graphite of (1) moderate purity as 99.5% as raw material, taking by weighing step (1) moderate purity and be 99.5% graphite 1g adds in the mixing solutions that is comprised of the 90ml vitriol oil (massfraction is 98%) and 30ml concentrated nitric acid (massfraction is 65%), placing frozen water to mix under the bath environment in mixture stirred 20 minutes, in mixture, add 8g potassium permanganate at leisure again, stirred 1 hour, then with mixture heating up to 75 ℃ and kept 30 minutes, adding afterwards the 92ml deionized water continued 85 ℃ of lower maintenances 30 minutes, add at last 10ml superoxol (massfraction 30%), stirred 10 minutes, mixture is carried out suction filtration, with 100ml dilute hydrochloric acid and 150ml deionized water solids is washed respectively successively again, wash altogether three times, last solid matter drying in 60 ℃ of vacuum drying ovens obtained graphite oxide in 12 hours.
In step (3), the graphite oxide adding deionized water with preparation in (2), the concentration of graphite oxide in water is 1mg/ml, mixture to graphite oxide and water carries out ultrasonic, ultrasonic power is 600W, 1.5 after hour mixture is carried out suction filtration, place 60 ℃ vacuum drying oven to dry by the fire 12 hours solid matter, obtain graphene oxide.
Step (4), graphene oxide and the F127 that obtains in (3) added (graphene oxide: F127: ether=1g: 3g: 1.5L) in the ether solvent successively, stirred 2 hours, mixing solutions is placed stink cupboard, after solvent evaporates, obtain graphene oxide/F127 mixture.
Step (5), the graphene oxide that obtains in (4)/F127 mixture is placed under ammonia (flow is 150ml/min)/argon gas (flow is 250ml/min) atmosphere, with the temperature rise rate of 10 ℃/min the envrionment temperature of graphene oxide/F127 mixture is risen to 800 ℃ from room temperature, and maintenance 30min, temperature is down to room temperature naturally under argon gas (flow is 200ml/min) mixed atmosphere at last, obtains nitrogen-doped graphene.
Embodiment 3
Step (1), purity is provided is 99.5% graphite.
Step (2), take the graphite of (1) moderate purity as 99.5% as raw material, taking by weighing step (1) moderate purity and be 99.5% graphite 1g adds in the mixing solutions that is comprised of the 93ml vitriol oil (massfraction is 98%) and 27ml concentrated nitric acid (massfraction is 65%), placing frozen water to mix under the bath environment in mixture stirred 20 minutes, in mixture, add 5g potassium permanganate at leisure again, stirred 1 hour, then with mixture heating up to 75 ℃ and kept 30 minutes, adding afterwards the 92ml deionized water continued 85 ℃ of lower maintenances 30 minutes, add at last 10ml superoxol (massfraction 30%), stirred 10 minutes, mixture is carried out suction filtration, with 100ml dilute hydrochloric acid and 150ml deionized water solids is washed respectively successively again, wash altogether three times, last solid matter drying in 60 ℃ of vacuum drying ovens obtained graphite oxide in 12 hours.
In step (3), the graphite oxide adding deionized water with preparation in (2), the concentration of graphite oxide in water is 1mg/ml, mixture to graphite oxide and water carries out ultrasonic, ultrasonic power is 500W, after 2 hours mixture is carried out suction filtration, place 60 ℃ vacuum drying oven to dry by the fire 12 hours solid matter, obtain graphene oxide.
Step (4), graphene oxide and the F127 that obtains in (3) added (graphene oxide: F127: ether=1g: 2g: 1.5L) in the ether solvent successively, stirred 2 hours, mixing solutions is placed stink cupboard, after solvent evaporates, obtain graphene oxide/F127 mixture.
Step (5), the graphene oxide that obtains in (4)/F127 mixture is placed under ammonia (flow is 300ml/min)/argon gas (flow is 200ml/min) atmosphere, with the temperature rise rate of 10 ℃/min the envrionment temperature of graphene oxide/F127 mixture is risen to 800 ℃ from room temperature, and maintenance 30min, temperature is down to room temperature naturally under argon gas (flow is 200ml/min) mixed atmosphere at last, obtains nitrogen-doped graphene.
Embodiment 4
Step (1), purity is provided is 99.5% graphite.
Step (2), take the graphite of (1) moderate purity as 99.5% as raw material, taking by weighing step (1) moderate purity and be 99.5% graphite 1g adds in the mixing solutions that is comprised of the 95ml vitriol oil (massfraction is 98%) and 20ml concentrated nitric acid (massfraction is 65%), placing frozen water to mix under the bath environment in mixture stirred 20 minutes, in mixture, add 3g potassium permanganate at leisure again, stirred 1 hour, then with mixture heating up to 75 ℃ and kept 30 minutes, adding afterwards the 92ml deionized water continued 85 ℃ of lower maintenances 30 minutes, add at last 10ml superoxol (massfraction 30%), stirred 10 minutes, mixture is carried out suction filtration, with 100ml dilute hydrochloric acid and 150ml deionized water solids is washed respectively successively again, wash altogether three times, last solid matter drying in 60 ℃ of vacuum drying ovens obtained graphite oxide in 12 hours.
In step (3), the graphite oxide adding deionized water with preparation in (2), the concentration of graphite oxide in water is 1mg/ml, mixture to graphite oxide and water carries out ultrasonic, ultrasonic power is 700W, after 2 hours mixture is carried out suction filtration, place 60 ℃ vacuum drying oven to dry by the fire 12 hours solid matter, obtain graphene oxide.
Step (4), graphene oxide and the F127 that obtains in (3) added (graphene oxide: F127: ether=1g: 1g: 1.5L) in the ether solvent successively, stirred 2 hours, mixing solutions is placed stink cupboard, after solvent evaporates, obtain graphene oxide/F127 mixture.
Step (5), the graphene oxide that obtains in (4)/F127 mixture is placed under ammonia (flow is 300ml/min)/argon gas (flow is 250ml/min) atmosphere, with the temperature rise rate of 10 ℃/min the envrionment temperature of graphene oxide/F127 mixture is risen to 800 ℃ from room temperature, and maintenance 30min, temperature is down to room temperature naturally under argon gas (flow is 200ml/min) mixed atmosphere at last, obtains nitrogen-doped graphene.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.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. the preparation method of a nitrogen-doped graphene is characterized in that, comprises the steps:
Graphite oxide is scattered in the deionized water, carries out supersound process, then suction filtration is dried, and obtains graphene oxide;
Described graphene oxide and Pluronic F-127 are added in the ether solvent successively, stirred 2～4 hours, solvent flashing obtains graphene oxide/Pluronic F-127 mixture;
Described graphene oxide/Pluronic F-127 mixture is placed under the mixed gas atmosphere of rare gas element and ammonia, be heated to 800～1000 ℃ with 5～20 ℃/minute temperature rise rates, 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: the method for the standby graphite oxide of described improved Hummers legal system is: graphite is added in the mixing solutions of the vitriol oil and concentrated nitric acid, mix stirring in the bath at frozen water, in mixing solutions, add potassium permanganate more afterwards, graphite is carried out oxidation, then mixing solutions is heated to 70～95 ℃ of insulations, graphite is further carried out oxidation, add at last hydrogen peroxide and remove potassium permanganate, suction filtration, with dilute hydrochloric acid and deionized water solids is carried out repetitive scrubbing, drying obtains graphite oxide.
3. the preparation method of nitrogen-doped graphene according to claim 2, it is characterized in that: the volume ratio of the described vitriol oil and concentrated nitric acid is 90～95: 20～30; The mass ratio of described graphite and potassium permanganate is 1: 3～10.
4. the preparation method of nitrogen-doped graphene according to claim 1, it is characterized in that: the mass ratio of described graphite oxide and described Pluronic F-127 is 1: 1～4.
5. the preparation method of nitrogen-doped graphene according to claim 1, it is characterized in that: the molecular weight of described Pluronic F-127 is 12500.
6. the preparation method of nitrogen-doped graphene according to claim 1, it is characterized in that: described graphite is that purity is 99.5% graphite.
7. the preparation method of nitrogen-doped graphene according to claim 1, it is characterized in that: the ultrasonic power of described supersound process is 500～800W, the time is 1～2 hour.
8. the preparation method of nitrogen-doped graphene according to claim 1, it 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, it 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: described graphene oxide and Pluronic F-127 are added in the step in the ether solvent successively, and every gram graphene oxide joins in the ether solvent of 1.5～2L.
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| CN106698410A (en) * | 2016-12-05 | 2017-05-24 | 四川大学 | Method for preparing nitrogen-atom doped carbon nanomaterial |
| CN107364845A (en) * | 2017-08-25 | 2017-11-21 | 广西大学 | A kind of method for preparing nitrogen-doped graphene |
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