CN106882794A - A kind of preparation method of nitrogen-doped graphene - Google Patents
A kind of preparation method of nitrogen-doped graphene Download PDFInfo
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- CN106882794A CN106882794A CN201710184461.2A CN201710184461A CN106882794A CN 106882794 A CN106882794 A CN 106882794A CN 201710184461 A CN201710184461 A CN 201710184461A CN 106882794 A CN106882794 A CN 106882794A
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- nitrogen
- doped graphene
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
The invention discloses a kind of preparation method of nitrogen-doped graphene, the nitrogen-doped graphene is with solid-state carbon source and indigo as raw material, said mixture is placed under atmosphere of inert gases by after effective combination drying, intensification is heated to 500~1500 DEG C, insulation is cooled to room temperature after a period of time, obtains the Graphene of N doping.Preparation process is simple of the invention, raw materials used cheap environmental protection, it is easy to industrial volume production.
Description
Technical field
The present invention relates to a kind of preparation method of nitrogen-doped graphene.
Background technology
Graphene is monoatomic layer carbon crystal material, and its discovery confirms the stable existence of two-dimensional material and opens
The new stage of the research of two-dimensional material, particularly its excellent photoelectric properties cause the interest of numerous scientists, such as it
Carrier mobility can reach 200,000cm2/ V.s, this provides the foundation for the electronics of manufacture high-frequency operation；Individual layer stone
Black alkene is 2.3% to the absorptivity of visible ray, and this enables that it turns into a kind of important materials of photoelectric device research.Graphene
High-specific surface area and good electric conductivity are also Graphene, and applying in terms of the energy storage devices such as lithium battery, ultracapacitor provides
Wide prospect.In order to more preferably be applied in photoelectric field and energy storage field, we must adjust the carrier of Graphene
Concentration, nitrogen is mixed in Graphene can change the electronic structure of Graphene, the electron concentration in lifting Graphene.Pass through
Changing the nitrogen content in Graphene can change the carrier concentration of Graphene, be widely used in ultracapacitor, lithium battery just
The fields such as pole additive, solar cell.Traditional nitrogen-doped graphene preparation method mainly has two kinds, and one kind is arc discharge
Method, another kind is chemical vapour deposition technique, and both approaches are operationally complex.
The content of the invention
It is an object of the invention to provide a kind of easy to operate, raw material environmental protection, the nitrogen for being capable of large-scale production and application
The preparation method of doped graphene.
The preparation method of nitrogen-doped graphene of the invention, comprises the following steps：
1) by required carbon source and it is indigo be well mixed in dispersion solvent, be adequately mixed after drying that to obtain mixing solid
Body；Wherein carbon source and indigo mass ratio are 1000:1~10:1.
2) above-mentioned hybrid solid is put into tube furnace, is sealed, then pass to protective gas, be warming up to 500~1500 DEG C,
Preferably, wherein heating rate is 1~200 DEG C/min, 1min~1000min is incubated.
3) room temperature is subsequently cooled to, nitrogen-doped graphene is obtained.
Heretofore described carbon source be one kind in Graphene, graphene oxide, polystyrene, PMMA and polyethylene or
It is various.Described dispersion solvent can use water or alcohol or acetone or isopropanol.
Step 2 of the present invention) described in protective gas be argon gas, nitrogen, helium or any two kinds and above gas by
The mixed gas of arbitrary proportion.
Step 2 of the present invention) in protective gas flow be 1sccm~500sccm, after protective gas is passed through, tube furnace is opened
Begin to heat up, wherein 1~200 DEG C/min of heating rate.
Step 3 of the present invention) in be cooled to room temperature rate of temperature fall be 1~1000 DEG C/min.
The present invention has the advantage that：
The present invention can obtain nitrogen-doped graphene by a solid phase thermal cracking, compared with traditional process, system
Standby process is simple, raw materials used cheap environmental protection, and the support of substrate is not needed in preparation process, it is easy to large-scale production.
Brief description of the drawings
Fig. 1 is shape appearance figure of the nitrogen-doped graphene of embodiment 1 under transmission electron microscope；
Fig. 2 is the x-ray photoelectron energy spectrum diagram of the nitrogen-doped graphene of embodiment 1；
Fig. 3 is the Raman spectrogram of the nitrogen-doped graphene of embodiment 1；
Fig. 4 is the shape appearance figure under the transmission electron microscope of the nitrogen-doped graphene of embodiment 2；
Fig. 5 is the shape appearance figure under the ESEM of the nitrogen-doped graphene of embodiment 2.
Specific embodiment
It is described further with reference to embodiments.
Embodiment 1：
1) by graphene powder and indigo according to mass ratio 10:1 is weighed, and is well mixed in water, is adequately mixed
Graphene/indigo mixture is obtained after drying.
2) above-mentioned hybrid solid is put into the quartz boat of tube furnace, protection gas is passed through by 200sccm of flow after sealing
Body argon gas, starts to be warming up to 1500 DEG C with the heating rate of 10 DEG C/min, is incubated 100min.
3) room temperature and then with 10 DEG C/min is cooled to, nitrogen-doped graphene is obtained.The nitrogen-doped graphene for obtaining is in Electronic Speculum
Under shape appearance figure as shown in Figure 1, accompanying drawing 2 is the x-ray photoelectron energy spectrum diagram of the nitrogen-doped graphene of embodiment 1, shows nitrogen
Atom is come into Graphene lattice；Accompanying drawing 3 is the Raman spectrogram of nitrogen-doped graphene, it is seen that its Raman G peaks exist
1587cm-1Near, and the graphite Raman G peaks of undoped p are in 1580cm-1, this Graphene for showing to obtain is that nitrogen replacement position is mixed
Miscellaneous Graphene.May determine that synthesized solid is nitrogen-doped graphene by accompanying drawing 2,3.X-ray photoelectron energy spectrum diagram is corresponding
Quantitative analysis shows that N doping content is 1.5%.
Embodiment 2：
1) by graphene oxide powder and indigo according to mass ratio 50:1 is weighed, and is then well mixed in alcohol,
It is adequately mixed after drying and obtains Graphene/indigo mixture.
2) above-mentioned hybrid solid is put into the quartz boat of tube furnace, protection gas is passed through by 200sccm of flow after sealing
Body argon gas, starts to be warming up to 1000 DEG C with the heating rate of 10 DEG C/min, and insulation 2 hours is simultaneously passed through argon gas protection.
3) room temperature and then with 50 DEG C/min is cooled to, nitrogen-doped graphene is obtained.The nitrogen-doped graphene for obtaining is in Electronic Speculum
Under shape appearance figure as shown in accompanying drawing 4,5.
Embodiment 3：
1) by PMMA and indigo according to mass ratio 500:1 is weighed, and is then well mixed in acetone, is adequately mixed
Bluish violet solid is obtained after drying.
2) above-mentioned bluish violet hybrid solid is put into the quartz boat of tube furnace, argon gas is passed through after sealing as whole process protection
Gas, argon flow amount is 200sccm, is to slowly warm up to 1000 DEG C, and wherein heating rate is 8 DEG C, is incubated 2 hours.
3) room temperature and then with 100 DEG C/min is cooled to, nitrogen-doped graphene is obtained.
Embodiment 4
1) by PMMA and indigo according to mass ratio 100:1 is weighed, and is then well mixed in isopropanol, through fully mixed
Close and obtain bluish violet solid after drying.
2) above-mentioned bluish violet hybrid solid is put into the quartz boat of tube furnace, argon gas is passed through after sealing as whole process protection
Gas, argon flow amount is 100sccm, is to slowly warm up to 500 DEG C, and wherein heating rate is 8 DEG C/min, is incubated 3 hours.
3) room temperature and then with 10 DEG C/min is cooled to, nitrogen-doped graphene is obtained.
Claims (6)
1. a kind of preparation method of nitrogen-doped graphene, it is characterised in that the method comprises the following steps：
1) by carbon source and it is indigo in dispersion solvent be well mixed；
2) well mixed hybrid solid is obtained after above-mentioned solution is dried；
3) above-mentioned hybrid solid is warming up to 500~1500 DEG C under protective gas protection, insulation a period of time, is subsequently cooled to
Room temperature, obtains nitrogen-doped graphene.
2. the preparation method of nitrogen-doped graphene according to claim 1, it is characterised in that described carbon source is graphite
At least one in alkene, graphene oxide, polystyrene, PMMA, polyethylene.
3. the preparation method of nitrogen-doped graphene according to claim 1, it is characterised in that described dispersion solvent is water
Or alcohol or acetone or isopropanol.
4. the preparation method of nitrogen-doped graphene according to claim 1, it is characterised in that described protective gas is argon
Gas, nitrogen, helium or wherein any multiple gases mixed gas in any proportion.
5. the preparation method of nitrogen-doped graphene according to claim 1, it is characterised in that step 3) in, described liter
It is 1~200 DEG C/min that temperature uses heating rate, insulation duration 1min~1000min.
6. the preparation method of nitrogen-doped graphene according to claim 1, it is characterised in that described carbon source and indigo
Mass ratio is 1000:1~10:1.
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Citations (7)
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|---|---|---|---|---|
| CN102120572A (en) * | 2011-01-24 | 2011-07-13 | 南京大学 | Method for preparing nitrogen-doped graphene |
| CN103172057A (en) * | 2013-03-07 | 2013-06-26 | 华南理工大学 | Preparation method of nitrogen and sulfur co-doped graphene |
| CN104229789A (en) * | 2014-09-25 | 2014-12-24 | 上海交通大学 | Preparation method of nitrogen-doped graphene |
| CN104760951A (en) * | 2015-04-09 | 2015-07-08 | 新疆大学 | Preparation method of nitrogen-doped graphene |
| CN104860312A (en) * | 2015-05-27 | 2015-08-26 | 上海理工大学 | Preparation method for corrugated nitrogen-doped graphene |
| CN105236399A (en) * | 2015-10-14 | 2016-01-13 | 上海大学 | Nitrogen-doped graphene hollow microsphere (NGHM) preparation method |
| CN103626158B (en) * | 2012-08-23 | 2016-04-06 | 中国科学院宁波材料技术与工程研究所 | The preparation method of nitrogen-doped graphene and application thereof |
-
2017
- 2017-03-24 CN CN201710184461.2A patent/CN106882794A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102120572A (en) * | 2011-01-24 | 2011-07-13 | 南京大学 | Method for preparing nitrogen-doped graphene |
| CN103626158B (en) * | 2012-08-23 | 2016-04-06 | 中国科学院宁波材料技术与工程研究所 | The preparation method of nitrogen-doped graphene and application thereof |
| CN103172057A (en) * | 2013-03-07 | 2013-06-26 | 华南理工大学 | Preparation method of nitrogen and sulfur co-doped graphene |
| CN104229789A (en) * | 2014-09-25 | 2014-12-24 | 上海交通大学 | Preparation method of nitrogen-doped graphene |
| CN104760951A (en) * | 2015-04-09 | 2015-07-08 | 新疆大学 | Preparation method of nitrogen-doped graphene |
| CN104860312A (en) * | 2015-05-27 | 2015-08-26 | 上海理工大学 | Preparation method for corrugated nitrogen-doped graphene |
| CN105236399A (en) * | 2015-10-14 | 2016-01-13 | 上海大学 | Nitrogen-doped graphene hollow microsphere (NGHM) preparation method |
Non-Patent Citations (1)
| Title |
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| SHENG Z H ET AL.: "Catalyst-free synthesis of nitrogen-doped graphene via thermal annealing graphite oxide with melamine and its excellent electrocatalysis", 《ACS NANO》 * |
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Application publication date: 20170623 |