CN106904604A - A kind of carbon aerogels and preparation method thereof - Google Patents
A kind of carbon aerogels and preparation method thereof Download PDFInfo
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- CN106904604A CN106904604A CN201510961329.9A CN201510961329A CN106904604A CN 106904604 A CN106904604 A CN 106904604A CN 201510961329 A CN201510961329 A CN 201510961329A CN 106904604 A CN106904604 A CN 106904604A
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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
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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
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
Abstract
A kind of carbon aerogels, N element is contained in the carbon aerogels, while also containing one or more in heterogeneous element P, S, B.One or more total mass content in the carbon aerogels in the content of N element and described heterogeneous element P, S, B is respectively 2% 7%.Compared with prior art, the invention has the advantages that：The prices of raw materials are cheap in preparation process, preparation process is simple, without the harsh preparation condition such as freeze-drying, be suitable to large-scale production.The carbon aerogels for preparing simultaneously have larger surface area, and good pore structure makes it have good application prospect in the field such as the conversion of energy and storage, absorption, sensor and adiabatic heat-insulation.
Description
Technical field
The present invention relates to carbon material preparation field, and in particular to a kind of carbon aerogels and preparation method thereof.
Background technology
Carbon aerogels, as a kind of new carbon material, with light weight, specific surface area is big, pore volume is big,
The low feature of thermal conductivity, in absorption, the conversion of energy and the field such as storage, sensor and heat-insulating material
Have a wide range of applications.
The preparation of carbon aerogels typically use sol-gal process or template-directing method, but the former typically to use it is cold
It is lyophilized it is dry keep skeleton structure to remove the solvent in gel, preparation condition is harsh；The latter depends on template
Fine structure and size, it is difficult to be prepared on a large scale, simply can the carbon aerogels preparation method of mass be still
The significant challenge in materials synthesis field, by scientific research institution and the extensive concern of enterprise.
The content of the invention
A kind of deficiency of the present invention for the existing technology of preparing of carbon aerogels, it is proposed that simple carbon aerogels material
Preparation method, the present invention realized using scheme in detail below：
A kind of carbon aerogels, N element is contained in the carbon aerogels, at the same also containing heterogeneous element P, S,
One or more in B.
The mass content of N element is 1%-7% in the carbon aerogels, in described heterogeneous element P, S, B
One or more total mass content is 1%-5%.
The carbon aerogels are the structure being cross-linked into by porous graphite flake layer, contain micropore, mesoporous and macropore；
The macropore by graphite flake layer stacking form, it is described it is mesoporous be distributed on graphite flake layer, the micropore is present in stone
On the mesoporous wall of ink sheet layer.
Between 0.5nm-2nm, mesopore size is distributed between 3nm-10nm the pore size distribution,
Big pore size distribution is between 50nm-100nm；
The specific surface area of the carbon aerogels is 1200-2000m2g-1；The specific surface of micropore in the carbon aerogels
Product accounts for the 50%-80% of total specific surface area.
The total pore volume of the carbon aerogels is 1.5-3m3g-1；The Micropore volume accounts for the 40%-90% of total pore volume,
Macropore and mesoporous pore volume account for the 10%-60% of total pore volume.
The preparation method of the carbon aerogels, comprises the following steps,
(1) preparation of carbon aerogels precursor：After polyalcohol and inorganic acid are stirred and heat and vacuumize and make it
Generation esterification, will contain amino-compound dispersion liquid add gained product in, again be well mixed after
Heating brings it about salt-forming reaction, obtains carbon aerogels precursor；
(2) preparation of carbon aerogels：It is the carbonization of inert atmosphere high temperature by step (1) gained carbon aerogels precursor
Treatment, obtains carbon aerogels.
Polyalcohol described in step (1) is 2 with the ratio of the amount of the material of inorganic acid：1-1：8；The inorganic acid with
The ratio of the amount of the material of amino-compound is 5：1-1：5.
The polyalcohol described in step (1) be pentaerythrite, xylitol, sorbierite in one or more；
The inorganic acid be boric acid, phosphoric acid, sulfuric acid, nitric acid in one or more；The amino-compound is urine
In element, melamine, cyanamide one or more；Solvent is methyl alcohol, ethanol and ethylene glycol or two kinds and two
Plant liquid mixed above.
The condition of esterification is that 0.5-5h is reacted at 70-200 DEG C described in step (1), and vacuum is
0.03-0.2Mpa；The salt-forming reaction condition be 30-150 DEG C at a temperature of react 2-24h.
It with heating rate is 2-10 DEG C/min that carbonization treatment condition described in step (2) is, is warming up to 300-600 DEG C
And 0.5-3h is kept, and high-temperature is risen to 700-1100 DEG C by 2-10 DEG C/min of heating rate again, keep this temperature
Degree 0.5-3h, is cooled to room temperature.
Inert gas described in step (2) is one or two gaseous mixture in nitrogen, argon gas.
Compared with prior art, the invention has the advantages that：In preparation process the prices of raw materials it is cheap, prepare
Process is simple, the preparation condition without the harshness such as freeze-drying, appetite large-scale production.The carbon gas for preparing simultaneously
Gel has larger surface area, and good pore structure makes it equal with field of storage with the conversion of energy in absorption
There is larger potential application foreground.
Brief description of the drawings
Fig. 1：The digital photograph of the carbon aerogels in embodiment 1；
Fig. 2：The SEM photograph of the carbon aerogels in embodiment 1；
Fig. 3：The TEM photos of the carbon aerogels in embodiment 1；
Fig. 4：The SEM photograph of the carbon aerogels in embodiment 2；
Fig. 5：The physical absorption curve of the carbon aerogels in embodiment 3；
Fig. 6：The pore size distribution curve of the carbon aerogels in embodiment 3.
Specific embodiment
Embodiment 1
6.8g pentaerythrites are weighed in flask, 29.40g phosphoric acid is added, (vacuum is 0.1MPa) are depressurized in stirring,
120 DEG C are heated to, 1.5h is incubated, the thick pentaerythritol phosphate liquid of pale yellow transparent is obtained.In another circle
120mL ethanol and 16.38g melamines are added in the flask of bottom, 1.5h is sufficiently stirred for, synthesis in upper step is obtained
Pentaerythritol phosphate pour into the melamine equipped with alcohol dispersant, be heated to 80 DEG C, be stirred at reflux 6h,
White emulsion is obtained, the big white solid of rotary evaporation by white solid, is put in quartz boat, in blanket of nitrogen
Under enclosing, the heating rate of 5 DEG C/min is warming up to 350 DEG C, keeps 0.5h, continues with the intensification speed of 5 DEG C/min
Rate is warming up to 900 DEG C, keeps 2h, is cooled to room temperature taking-up.The digital photograph of its exterior appearance is shown in accompanying drawing 1,
Microscopic appearance SEM photograph is shown in accompanying drawing 2, transmits electric competing photo and sees accompanying drawing 3.It can be seen that outward appearance is foam
The solid of shape, quality is very light, and SEM display microstructures are that graphite flake layer stacking is formed, TEM display stones
There is a large amount of mesoporous, and mesoporous interconnection on ink sheet layer.
Embodiment 2
13.6g pentaerythrites are weighed in flask, add 29.40g phosphoric acid, (vacuum is for stirring decompression
0.1MPa), 120 DEG C are heated to, 1.5h is incubated, the thick pentaerythritol phosphate liquid of pale yellow transparent is obtained.
120mL ethanol and 16.38g melamines are added in another round-bottomed flask, 1.5h is sufficiently stirred for, by upper step
The pentaerythritol phosphate that synthesis is obtained is poured into the melamine equipped with alcohol dispersant, is heated to 80 DEG C, is stirred
Backflow 6h is mixed, white emulsion is obtained, the big white solid of rotary evaporation, by white solid, is put in quartz boat,
Under nitrogen atmosphere, the heating rate of 5 DEG C/min is warming up to 350 DEG C, keeps 0.5h, continues with 5 DEG C/min
Heating rate be warming up to 900 DEG C, keep 2h, be cooled to room temperature taking-up.Its microscopic appearance SEM is shown in accompanying drawing
4.It can be seen that SEM display microscopic appearances are graphite platelet structure, graphite flake layer thickness is 300-400nm
Left and right.
Embodiment 3
6.8g pentaerythrites are weighed in flask, 29.40g phosphoric acid is added, (vacuum is 0.1MPa) are depressurized in stirring,
120 DEG C are heated to, 1.5h is incubated, the thick pentaerythritol phosphate liquid of pale yellow transparent is obtained.In another circle
120mL ethanol and 16.38g melamines are added in the flask of bottom, 1.5h is sufficiently stirred for, synthesis in upper step is obtained
Pentaerythritol phosphate pour into the melamine equipped with alcohol dispersant, be heated to 80 DEG C, be stirred at reflux 6h,
White emulsion is obtained, the big white solid of rotary evaporation by white solid, is put in quartz boat, in blanket of nitrogen
Under enclosing, the heating rate of 5 DEG C/min is warming up to 350 DEG C, keeps 0.5h, continues with the intensification speed of 5 DEG C/min
Rate is warming up to 1000 DEG C, keeps 2h, is cooled to room temperature taking-up.Its physical absorption curve is shown in accompanying drawing 5, aperture
Distribution curve is shown in accompanying drawing 6. it can be seen that there is back stagnant ring in physical absorption curve, shows there be mesoporous depositing
, specific surface area is thus calculated for 1717m2/g, its pore-size distribution is simulated by DFT, its hole
There are two integrated distributions of pore diameter range in footpath, one is that, less than the micropore of two nanometers, another receives for 3-8
Rice it is mesoporous.
Claims (9)
1. a kind of carbon aerogels, it is characterised in that：Contain N element in the carbon aerogels, while also containing
One or more in heterogeneous element P, S, B.
2. carbon aerogels as claimed in claim 1, it is characterised in that：The matter of N element in the carbon aerogels
Amount content is 1%-7%, one or more the total mass content in described heterogeneous element P, S, B
It is 1%-5%.
3. carbon aerogels as claimed in claim 1, it is characterised in that：The carbon aerogels are by porous graphite
Lamella crosslinking is formed, and contains micropore, mesoporous and macroporous structure；The macropore is formed by graphite flake layer stacking, institute
Pore size distribution is given an account of on graphite flake layer, the micropore is present on the mesoporous wall of graphite flake layer.
4. carbon aerogels as claimed in claim 3, it is characterised in that：The total pore volume of the carbon aerogels is 1.5
-3m3g-1；The Micropore volume accounts for the 40%-90% of total pore volume, and macropore and mesoporous pore volume account for total pore volume
10%-60%.
5. the preparation method of any carbon aerogels of a kind of claim 1-4, it is characterised in that：Including with
Lower step,
(1) preparation of carbon aerogels precursor：Stirring and heat to vacuumize polyalcohol and inorganic acid sends out it
Raw esterification, reaction is finished in the dispersion liquid addition gained product containing amino-compound, is mixed again
It is uniform and heat and bring it about salt-forming reaction, obtain carbon aerogels precursor；
(2) preparation of carbon aerogels：It is the carbonization of nitrogen atmosphere high temperature by step (1) gained carbon aerogels precursor
Treatment, obtains carbon aerogels.
6. the preparation method of carbon aerogels as claimed in claim 5, it is characterised in that：It is many described in step (1)
First alcohol is 2 with the ratio of the amount of the material of inorganic acid：1-1：8；The inorganic acid and the material of amino-compound
The ratio of amount is 5：1-1：5.
7. the preparation method of carbon aerogels as claimed in claim 5, it is characterised in that：It is molten described in step (1)
Agent is water, methyl alcohol, ethanol, ethylene glycol or two kinds and two or more mixed liquors；The polyalcohol is Ji Wusi
In alcohol, xylitol, sorbierite one or more；The inorganic acid is boric acid, phosphoric acid, sulfuric acid, nitric acid
In one or more；The amino-compound be it is a kind of in urea, melamine, cyanamide, amino acid or
It is two or more；The solvent of the dispersion liquid is the mixed of one or two and the above in methyl alcohol, ethanol or ethylene glycol
Close liquid.
8. the preparation method of carbon aerogels as claimed in claim 5, it is characterised in that：Ester described in step (1)
The condition for changing reaction is to react 0.5-5h at 70-200 DEG C；Vacuum is 0.03-0.2Mpa, described anti-into salt
Condition is answered to react 2-24h at a temperature of 30-150 DEG C.
9. the preparation method of carbon aerogels as claimed in claim 5, it is characterised in that：Carbon described in step (2)
Change treatment conditions to be with heating rate is 2-10 DEG C/min, from room temperature to 300-600 DEG C and keeps 0.5-3h,
High-temperature is risen to 700-1100 DEG C by 2-10 DEG C/min of heating rate again, this temperature 0.5-3h is kept, and is cooled down
To room temperature.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108394882A (en) * | 2018-03-08 | 2018-08-14 | 中国检验检疫科学研究院 | A kind of ultralight porous carbon materials and preparation method thereof |
| CN108609607A (en) * | 2018-07-26 | 2018-10-02 | 中国科学技术大学 | A kind of carbon aerogels and preparation method thereof with superhigh specific surface area |
| CN109464968A (en) * | 2018-12-06 | 2019-03-15 | 西华大学 | It is a kind of high at charcoal-aero gel and preparation method thereof, application |
| CN109956461A (en) * | 2017-12-14 | 2019-07-02 | 中国科学院大连化学物理研究所 | A kind of preparation of Porous hollow carbon nanosheet and application |
| CN113694892A (en) * | 2021-08-27 | 2021-11-26 | 伯克利南京医学研究有限责任公司 | Carbon aerogel composite structure, composite filter element, preparation methods of carbon aerogel composite structure and composite filter element, and application of carbon aerogel composite structure and composite filter element |
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| EP2687483A1 (en) * | 2012-07-16 | 2014-01-22 | Basf Se | Graphene containing nitrogen and optionally iron and/or cobalt |
| CN104245578A (en) * | 2012-03-09 | 2014-12-24 | 巴斯夫欧洲公司 | Aerogel based on doped graphene |
| CN104437279A (en) * | 2014-11-17 | 2015-03-25 | 北京大学 | Carbon doped nano tube aerogel and preparation method and application thereof |
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| WO2004009673A1 (en) * | 2002-07-22 | 2004-01-29 | Aspen Aerogels, Inc. | Polyimide aerogels, carbon aerogels, and metal carbide aerogels and methods of making same |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109956461A (en) * | 2017-12-14 | 2019-07-02 | 中国科学院大连化学物理研究所 | A kind of preparation of Porous hollow carbon nanosheet and application |
| CN108394882A (en) * | 2018-03-08 | 2018-08-14 | 中国检验检疫科学研究院 | A kind of ultralight porous carbon materials and preparation method thereof |
| CN108609607A (en) * | 2018-07-26 | 2018-10-02 | 中国科学技术大学 | A kind of carbon aerogels and preparation method thereof with superhigh specific surface area |
| CN108609607B (en) * | 2018-07-26 | 2020-10-27 | 中国科学技术大学 | Carbon aerogel with ultrahigh specific surface area and preparation method thereof |
| CN109464968A (en) * | 2018-12-06 | 2019-03-15 | 西华大学 | It is a kind of high at charcoal-aero gel and preparation method thereof, application |
| CN113694892A (en) * | 2021-08-27 | 2021-11-26 | 伯克利南京医学研究有限责任公司 | Carbon aerogel composite structure, composite filter element, preparation methods of carbon aerogel composite structure and composite filter element, and application of carbon aerogel composite structure and composite filter element |
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