CN109775692A - The preparation method of heteroatom doped graphene - Google Patents
The preparation method of heteroatom doped graphene Download PDFInfo
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- CN109775692A CN109775692A CN201711131950.8A CN201711131950A CN109775692A CN 109775692 A CN109775692 A CN 109775692A CN 201711131950 A CN201711131950 A CN 201711131950A CN 109775692 A CN109775692 A CN 109775692A
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Abstract
The invention discloses a kind of preparation methods of heteroatom doped graphene.The method is by the way that nitrogen source and carbon source to be dissolved in solvent in proportion, and stirring in water bath obtains collosol and gel, and high temperature sintering obtains nitrogen-doped graphene to the presoma after collosol and gel drying again.Meanwhile the doping of nitrogen sulphur, nitrogen boron or nitrogen phosphorus etc. may be implemented by materials containing other doped chemicals such as addition thiocarbamide, sulfuric acid, boric acid, ammonium borate, phosphoric acid, ammonium phosphate in raw material.The ratio that the present invention passes through adjusting nitrogen source and carbon source, control pyrolysis temperature and time, add content and type containing other controllable doping of nonmetalloid compound, obtain multielement codope graphene, the doped graphene material of preparation has high specific surface area, excellent electric conductivity, active site abundant, it can be used as electrode material, be used for electrochemical energy storage/conversion art.
Description
Technical field
The invention belongs to technical field of material, are related to a kind of preparation method of heteroatom doped graphene.
Background technique
Graphene is by carbon atom with sp2The monoatomic layer structure that hydridization is combined into, have stability is high, electric conductivity is strong,
The unique performances such as theoretical specific surface area is big.Graphene combination electrode material energy density with higher, while having smaller
Internal resistance, it can be achieved that high power charging-discharging.However weight heap easily occurs during making and using for single-layer graphene
Folded phenomenon causes its surface area to reduce, influences the chemical property of graphene.It is mixed in the perfect hexagonal carbon of pure graphene
The transmission speed for stacking again, generating defect in basal plane, generate band gap and accelerate charge of graphene can be prevented by entering hetero atom
Rate improves the performance of its electrochemistry.Incorporation unitary or be co-doped with the heteroatomic grapheme material of binary be widely used in lithium/sodium from
Sub- battery, supercapacitor and fuel cell.
It prepares heteroatom doped graphene at present and generally requires and first prepare graphene oxide or graphene, lead to again later
It crosses organic matter containing heteroatom and introduces heteroatom, mainly there is chemical vapor deposition (CVD) method, arc discharge method, high energy electric heating
Method, template etc..
Wherein CVD method is most widely used, and is reacted using chemical gas, and product reprecipitation is on substrate with system
Standby required substance.During using CVD method preparation nitrogen-doped graphene, carbon source and nitrogen source are provided using methane and ammonia
The redox reaction of high temperature occurs in special reacting furnace.The C that gaseous methane and ammonia generate after being reacted is in height
Also it is in gaseous state under temperature, substrate surface can be thinly attached to after encountering substrate.In C deposited atom during substrate, N atom
Also can be on C atom coprecipitation to substrate, the substance finally generated on substrate is exactly that nitrogen-atoms, carbon atom mixing are thin
Film, i.e. nitrogen-doped graphene film.But the residual air after the gas source and reaction due to CVD method participation deposition reaction has certain toxicity,
And reaction temperature is high, the requirement to base material and experimental facilities is also relatively high, therefore production cost is higher, is not suitable for scale
Change application.How the manufacturing cost of heteroatom doped graphene is reduced, and low cost produces heteroatom doped graphite in enormous quantities
Alkene becomes the bottleneck of doped graphene industrialization large-scale production.
Summary of the invention
To solve environmental pollution in existing heteroatom doped graphene preparation method, at high cost, complex process asking
Topic, the present invention provide the preparation method for the heteroatom doped graphene that one kind is controllable, inexpensive, can be mass-produced.
Technical scheme is as follows:
The preparation method of heteroatom doped graphene, by nitrogen source (urea, thiocarbamide, melamine, cyanuric trichloride, cyanamide,
Dicyanodiamine or other organic matters for heating producible graphite phase carbon nitride product) and carbon source (various carbohydrates or hydrocarbon
Deng) be dissolved in solvent in proportion, stirring in water bath obtains collosol and gel, and high temperature sintering obtains the presoma after collosol and gel drying again
Nitrogen-doped graphene.Meanwhile it being mixed by addition thiocarbamide, sulfuric acid, boric acid, ammonium borate, phosphoric acid, ammonium phosphate etc. containing other in raw material
The material of miscellaneous element realizes the doping of nitrogen sulphur, nitrogen boron or nitrogen phosphorus etc., the specific steps are as follows:
Step 1, it is 30:1~5:1 by the mass ratio of nitrogen source and carbon source, nitrogen source and carbon source is dissolved in solvent, 60~90 DEG C
Lower stirring in water bath, obtains collosol and gel, and the solvent is selected from water, ethyl alcohol or ethanol solution；
Step 2, collosol and gel is dried, 2~15h of high temperature sintering at 600~1200 DEG C obtains heteroatom doped graphite
Alkene.
Preferably, in step 1, the originals containing doped chemical such as thiocarbamide, sulfuric acid, boric acid, ammonium borate, phosphoric acid, ammonium phosphate are added
Material.
In step 1, the nitrogen source is selected from urea, thiocarbamide, melamine, cyanuric trichloride, cyanamide, dicyanodiamine or other
Heat one of organic matter for producing graphite phase carbon nitride product or a variety of.
In step 2, the drying temperature is 80~200 DEG C.
Preferably, in step 2, the sintering temperature is 750~850 DEG C, and the sintering time is 5h.
Compared with prior art, the invention has the following advantages that
(1) nitrogen source that graphite phase carbon nitride is produced using heating such as urea, on the one hand facilitates graphene layer structure
Formation, on the other hand can directly by nitrogen atom doping in graphene, compared to other two-step methods prepare heteroatom doping
The method of graphene, simplifies operating procedure, hence it is evident that reduces preparation cost；
(2) by the way that the raw material containing heteroatom is added in the solution, the doping of heteroatom, operation letter can be directly realized by
Just；
(3) raw material containing heteroatom releases gas (such as ammonia, hydrogen sulfide containing heteroatom during heating
Deng), in the forming process of graphene, heteroatom is entrained in situ inside graphene, it can be achieved that higher heteroatom
Doping content.
Doped graphene material prepared by the present invention has high specific surface area, excellent electric conductivity, activity abundant
Site can be used as electrode material, for energy storage fields such as lithium ion battery, sodium-ion battery, supercapacitors.
Detailed description of the invention
Fig. 1 is that the scanning electron microscope (SEM) photograph (a) of nitrogen-doped graphene product prepared by embodiment 1 and the nitrogen of the preparation of embodiment 1 are mixed
The scanning electron microscope (SEM) photograph (c) of the material of transmission electron microscope picture (b) and comparative example 1 preparation of miscellaneous graphite ene product.
The atomic force microscopy diagram (a) for the nitrogen-doped graphene product that Fig. 2 is prepared for embodiment 1 and corresponding Thickness Analysis
Scheme (b).
Fig. 3 is the XRD spectra (a) of nitrogen-doped graphene product prepared by embodiment 1 and the XPS high-resolution spectrogram of N1s
(b)。
Fig. 4 is the full spectrogram (b) of XRD (a) and XPS of nitrogen sulphur codope graphite ene product prepared by embodiment 3.
Fig. 5 is the scanning electron microscope (SEM) photograph of the scanning electron microscope (SEM) photograph (a) of product prepared by comparative example 2 and the product of the preparation of comparative example 3
(b)。
Specific embodiment
Below with reference to embodiment and attached drawing, the invention will be further described.
Embodiment 1
10g urea and 1g citric acid are dissolved in 100mL alcohol and the deionized mixed solution of 100mL, in 85 DEG C of water-baths
Stirring is to collosol and gel state, and by gained collosol and gel, 100 DEG C of dry 8h obtain presoma in an oven.Gained presoma is filled
Enter in quartz boat, 850 DEG C of heat preservation 5h are heated in tube furnace, room temperature is down to and obtains nitrogen-doped graphene.
From stereoscan photograph (see Fig. 1 a) it can be seen that prepared nitrogen-doped graphene is in uniform sheet.
Fig. 1 b is the transmission electron microscope photo of nitrogen-doped graphene, it can be seen that graphene sheet layer each section field color is equal
One, it is gauze-like.Fig. 2 is the atomic force microscopy diagram of nitrogen-doped graphene.From the figure it may be seen that the height of nitrogen-doped graphene
Degree is about 3nm.
From the XRD diagram (see Fig. 3 a) of product it is found that product has the diffraction maximum of widthization specific to graphene.Fig. 3 b is nitrogen
The high-resolution spectrogram of N element in the XPS test of doped graphene.By analysis it can be seen that N element is successfully doped to graphite
In olefinic carbon structure.
Embodiment 2
5g urea and 1g glucose are dissolved in 150mL alcohol and the deionized mixed solution of 100mL, stirred in 85 DEG C of water-baths
It mixes to collosol and gel state, by gained collosol and gel, 100 DEG C of dry 8h obtain presoma in an oven.Gained presoma is packed into
In quartz boat, it is heated to 750 DEG C of heat preservation 5h in tube furnace, is down to room temperature and obtains nitrogen-doped graphene.Obtained N doping stone
Black alkene and the obtained nitrogen-doped graphene of embodiment 1 have similar pattern.
Embodiment 3
10g urea and 1g citric acid and 5g thiocarbamide are dissolved in 100mL alcohol and the deionized mixed solution of 100mL,
85 DEG C of stirring in water bath are to collosol and gel state, and by gained collosol and gel, 100 DEG C of dry 8h obtain presoma in an oven.By gained
Presoma is fitted into quartz boat, and 1200 DEG C of heat preservation 2h are heated in tube furnace, is down to room temperature and is obtained nitrogen sulphur codope graphene.
The obtained nitrogen-doped graphene in nitrogen sulphur codope graphene and embodiment 1 has similar gauze-like pattern.Fig. 4 is total for nitrogen sulphur
The total spectrogram of XRD spectra and XPS of doped graphene, it can be seen that the successful doping of S.Pass through analysis, the atom of the N and S of doping
Percentage is respectively 20.52at% and 3.51at%.
Embodiment 4
30g urea and 1g sucrose are dissolved in 100mL deionized water, in 75 DEG C of stirrings to collosol and gel state, by gained
To collosol and gel 120 DEG C of dry 10h obtain presoma in an oven.Gained presoma is fitted into quartz boat, in tube furnace
In be heated to 600 DEG C of heat preservation 15h, be down to room temperature and obtain nitrogen-doped graphene.In obtained nitrogen-doped graphene and example 1
Nitrogen-doped graphene has similar microscopic appearance.
Comparative example 1
This comparative example is substantially the same manner as Example 1, unique the difference is that sintering temperature is 500 DEG C.Obtained product
As illustrated in figure 1 c, lamella is thicker for scanning electron microscopic picture, not the shape characteristic of graphene.
Comparative example 2
This comparative example is substantially the same manner as Example 4, unique the difference is that in 600 DEG C of heat preservation 1h of sintering temperature.It is obtained
The scanning electron microscopic picture of product is as shown in Figure 5 a, is bulk, not the shape characteristic of graphene.
Comparative example 3
This comparative example is substantially the same manner as Example 1, unique the difference is that without addition urea.The scanning of obtained product
Electron microscopic picture is as shown in Figure 5 b, is big bulk, not the shape characteristic of graphene.
Claims (5)
1. the preparation method of heteroatom doped graphene, which is characterized in that specific step is as follows:
Step 1, it is 30:1~5:1 by the mass ratio of nitrogen source and carbon source, nitrogen source and carbon source is dissolved in solvent, 60~90 DEG C are lauched
Bath stirring, obtains collosol and gel, and the solvent is selected from water, ethyl alcohol or ethanol solution；
Step 2, collosol and gel is dried, 2~15h of high temperature sintering at 600~1200 DEG C obtains heteroatom doped graphene.
2. preparation method according to claim 1, which is characterized in that in step 1, thiocarbamide, sulfuric acid, boric acid, boric acid is added
The raw material of ammonium, phosphoric acid or ammonium phosphate containing doped chemical.
3. preparation method according to claim 1, which is characterized in that in step 1, the nitrogen source be selected from urea, thiocarbamide,
Melamine, cyanuric trichloride, cyanamide, dicyanodiamine or other one heated in the organic matter for producing graphite phase carbon nitride product
Kind is a variety of.
4. preparation method according to claim 1, which is characterized in that in step 2, the drying temperature is 80~200
℃。
5. preparation method according to claim 1, which is characterized in that in step 2, the sintering temperature is 750~850
DEG C, the sintering time is 5h.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110272044A (en) * | 2019-07-25 | 2019-09-24 | 福建农林大学金山学院 | A kind of nitrogen phosphorus sulphur codope active carbon and preparation method thereof |
| CN110294477A (en) * | 2019-07-25 | 2019-10-01 | 福建农林大学金山学院 | A kind of nitrogen sulphur codope active carbon and preparation method thereof |
| CN110342513A (en) * | 2019-07-25 | 2019-10-18 | 福建农林大学 | A method of N doping granular activated carbon is prepared using melamine waste |
| CN110346430A (en) * | 2019-06-17 | 2019-10-18 | 福建师范大学 | A kind of Na+Adulterate g-C3N4Composite material, electrochemical sensor and preparation method thereof, purposes |
| CN110357096A (en) * | 2019-07-25 | 2019-10-22 | 福建农林大学 | It is a kind of based on alkali/urea dissolution system nitrating active carbon and preparation method thereof |
| CN110562961A (en) * | 2019-08-26 | 2019-12-13 | 广西大学 | Method for in-situ synthesis of nitrogen and sulfur co-doped stereo graphene |
| CN110911665A (en) * | 2019-11-21 | 2020-03-24 | 湖北工程学院 | Boron and nitrogen doped lithium ion battery negative electrode material and preparation method thereof |
| CN112366316A (en) * | 2020-09-27 | 2021-02-12 | 泰山学院 | Preparation method and application of nitrogen and phosphorus co-doped graphene |
| CN113812420A (en) * | 2021-10-12 | 2021-12-21 | 上海腾灵冷暖设备工程有限公司 | Rapid preparation method of boron nitride/carbon nitride/silver monatomic antibacterial agent |
| CN114583127A (en) * | 2022-02-28 | 2022-06-03 | 南京工业大学 | Method for preparing CoNi-S @3D-C nano composite material and modified battery diaphragm |
| CN115520856A (en) * | 2022-08-19 | 2022-12-27 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of nano composite material with elemental iodine and sulfur particles anchored in nitrogen-doped graphene axial plane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104229789A (en) * | 2014-09-25 | 2014-12-24 | 上海交通大学 | Preparation method of nitrogen-doped graphene |
| CN104710445A (en) * | 2013-12-15 | 2015-06-17 | 中国科学院大连化学物理研究所 | Boron and nitrogen codoped graphene, and preparation method and application thereof |
-
2017
- 2017-11-15 CN CN201711131950.8A patent/CN109775692A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104710445A (en) * | 2013-12-15 | 2015-06-17 | 中国科学院大连化学物理研究所 | Boron and nitrogen codoped graphene, and preparation method and application thereof |
| CN104229789A (en) * | 2014-09-25 | 2014-12-24 | 上海交通大学 | Preparation method of nitrogen-doped graphene |
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| CN110346430A (en) * | 2019-06-17 | 2019-10-18 | 福建师范大学 | A kind of Na+Adulterate g-C3N4Composite material, electrochemical sensor and preparation method thereof, purposes |
| CN110346430B (en) * | 2019-06-17 | 2021-06-04 | 福建师范大学 | Na+Doping with g-C3N4Composite material, electrochemical sensor, preparation method and application thereof |
| CN110357096A (en) * | 2019-07-25 | 2019-10-22 | 福建农林大学 | It is a kind of based on alkali/urea dissolution system nitrating active carbon and preparation method thereof |
| CN110342513B (en) * | 2019-07-25 | 2022-08-05 | 福建农林大学 | Method for preparing nitrogen-doped granular activated carbon by utilizing melamine waste |
| CN110272044A (en) * | 2019-07-25 | 2019-09-24 | 福建农林大学金山学院 | A kind of nitrogen phosphorus sulphur codope active carbon and preparation method thereof |
| CN110342513A (en) * | 2019-07-25 | 2019-10-18 | 福建农林大学 | A method of N doping granular activated carbon is prepared using melamine waste |
| CN110294477B (en) * | 2019-07-25 | 2022-08-05 | 福建农林大学金山学院 | Nitrogen-sulfur co-doped activated carbon and preparation method thereof |
| CN110294477A (en) * | 2019-07-25 | 2019-10-01 | 福建农林大学金山学院 | A kind of nitrogen sulphur codope active carbon and preparation method thereof |
| CN110272044B (en) * | 2019-07-25 | 2022-08-05 | 福建农林大学金山学院 | Nitrogen, phosphorus and sulfur co-doped active carbon and preparation method thereof |
| CN110357096B (en) * | 2019-07-25 | 2022-08-05 | 福建农林大学 | Nitrogen-doped activated carbon based on alkali/urea dissolving system and preparation method thereof |
| CN110562961A (en) * | 2019-08-26 | 2019-12-13 | 广西大学 | Method for in-situ synthesis of nitrogen and sulfur co-doped stereo graphene |
| CN110911665A (en) * | 2019-11-21 | 2020-03-24 | 湖北工程学院 | Boron and nitrogen doped lithium ion battery negative electrode material and preparation method thereof |
| CN112366316B (en) * | 2020-09-27 | 2022-03-01 | 泰山学院 | Preparation method and application of nitrogen and phosphorus co-doped graphene |
| CN112366316A (en) * | 2020-09-27 | 2021-02-12 | 泰山学院 | Preparation method and application of nitrogen and phosphorus co-doped graphene |
| CN113812420A (en) * | 2021-10-12 | 2021-12-21 | 上海腾灵冷暖设备工程有限公司 | Rapid preparation method of boron nitride/carbon nitride/silver monatomic antibacterial agent |
| CN114583127A (en) * | 2022-02-28 | 2022-06-03 | 南京工业大学 | Method for preparing CoNi-S @3D-C nano composite material and modified battery diaphragm |
| CN115520856A (en) * | 2022-08-19 | 2022-12-27 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of nano composite material with elemental iodine and sulfur particles anchored in nitrogen-doped graphene axial plane |
| CN115520856B (en) * | 2022-08-19 | 2024-06-11 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of nanocomposite with elemental iodine and sulfur particles anchored in axial plane of nitrogen-doped graphene |
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Application publication date: 20190521 |