CN106904604B - 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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- CN106904604B CN106904604B CN201510961329.9A CN201510961329A CN106904604B CN 106904604 B CN106904604 B CN 106904604B CN 201510961329 A CN201510961329 A CN 201510961329A CN 106904604 B CN106904604 B CN 106904604B
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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 contain N element in the carbon aerogels, while also containing one or more of heterogeneous element P, S, B.Total mass content of one or more of the content of N element and described heterogeneous element P, S, B are respectively 2%-7% in the carbon aerogels.Compared with prior art, the present invention has the advantage that the preparation condition that preparation process chinese raw materials is cheap, preparation process is simple, harsh without freeze-drying etc., is suitable for large-scale production.The carbon aerogels of preparation have biggish surface area simultaneously, and good pore structure makes it have good application prospect in the fields 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 fields, and in particular to a kind of carbon aerogels and preparation method thereof.
Background technique
Carbon aerogels, as a kind of novel carbon material, big with light weight, large specific surface area, pore volume, thermal conductivity
The features such as low, has a wide range of applications in the fields such as absorption, the conversion of energy and storage, sensor and heat-insulating material.
The preparation of carbon aerogels generally uses sol-gal process or template-directing method, however the former will generally use freezing and do
Dry to keep skeleton structure to remove the solvent in gel, preparation condition is harsh；The latter depends on the fine structure and ruler of template
It is very little, it is difficult to be prepared on a large scale, simply can the carbon aerogels preparation method of mass be still the great of materials synthesis field and choose
War, the extensive concern by scientific research institution and enterprise.
Summary of the invention
The present invention is directed to the deficiency of the existing technology of preparing of carbon aerogels, proposes a kind of system of simple carbon aerogels material
Preparation Method, the present invention are realized using scheme in detail below:
A kind of carbon aerogels contain N element in the carbon aerogels, while also containing one of heterogeneous element P, S, B
Or it is two or more.
The mass content of N element is 1%-7%, one of described heterogeneous element P, S, B or two in the carbon aerogels
Kind or more total mass content be 1%-5%.
The carbon aerogels are the structure being cross-linked by porous graphite flake layer, contain micropore, mesoporous and macropore；It is described big
Hole is stacked by graphite flake layer, it is described it is mesoporous be distributed on graphite flake layer, the micropore is present in the mesoporous wall of graphite flake layer
On.
Between 0.5nm-2nm, mesopore size is distributed between 3nm-10nm the pore size distribution, big pore size point
Cloth is between 50nm-100nm；
The specific surface area of the carbon aerogels is 1200-2000m2g-1；The specific surface area of micropore accounts in the carbon aerogels
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
The 10%-60% of total pore volume is accounted for mesoporous Kong Rong.
The preparation method of the carbon aerogels, includes the following steps,
(1) preparation of carbon aerogels precursor: polyalcohol and inorganic acid after mixing evenly and are heated and vacuumize and bring it about
Dispersion liquid containing amino-compound is added in gained reaction product esterification, and heating is brought it about after mixing again
Salt-forming reaction obtains carbon aerogels precursor；
(2) preparation of carbon aerogels: carbon aerogels precursor obtained by step (1) is at inert atmosphere high temperature carbonization
Reason, obtains carbon aerogels.
The ratio of the amount of the substance of polyalcohol described in step (1) and inorganic acid is 2:1-1:8；The inorganic acid and amination
The ratio for closing the amount of the substance of object is 5:1-1:5.
The polyalcohol described in step (1) is pentaerythrite, xylitol, one or more kinds of in sorbierite；It is described
Inorganic acid is boric acid, phosphoric acid, sulfuric acid, one or more kinds of in nitric acid；The amino-compound is urea, melamine, cyanogen
It is one or more kinds of in amine；Solvent is methanol, ethyl alcohol and ethylene glycol or two kinds and two or more mixed liquors.
The condition of esterification described in step (1) is that 0.5-5h, vacuum degree 0.03- are reacted at 70-200 DEG C
0.2Mpa；The salt-forming reaction condition reacts 2-24h at a temperature of being 30-150 DEG C.
It is 2-10 DEG C/min that carbonization treatment condition described in step (2), which is with heating rate, is warming up to 300-600 DEG C and protects
0.5-3h is held, is again that 2-10 DEG C/min increases temperature to 700-1100 DEG C with heating rate, keeps this temperature 0.5-3h, it is cooling
To room temperature.
Inert gas described in step (2) is nitrogen, gaseous mixture one or two kinds of in argon gas.
Compared with prior art, the present invention has the advantage that preparation process chinese raw materials is cheap, preparation process is simple
Preparation condition single, harsh without freeze-drying etc., appetite large-scale production.The carbon aerogels of preparation have biggish table simultaneously
Area, good pore structure make it have biggish potential application foreground with field of storage in absorption and the conversion of energy.
Detailed description of the invention
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 photo 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 pentaerythrite is weighed in flask, 29.40g phosphoric acid, stirring decompression (vacuum degree 0.1MPa), heating is added
To 120 DEG C, 1.5h is kept the temperature, the thick pentaerythritol phosphate liquid of pale yellow transparent is obtained.It is added in another round-bottomed flask
120mL ethyl alcohol and 16.38g melamine, are sufficiently stirred 1.5h, and the pentaerythritol phosphate synthesized in upper step is poured into dress
Have in the melamine of alcohol dispersant, be heated to 80 DEG C, be stirred at reflux 6h, obtains white emulsion, the great Bai of rotary evaporation
White solid is put in quartz boat by color solid, and under nitrogen atmosphere, the heating rate of 5 DEG C/min is warming up to 350 DEG C, is kept
0.5h is continued to be warming up to 900 DEG C with the heating rate of 5 DEG C/min, keeps 2h, be cooled to room temperature taking-up.The number of its exterior appearance
Code photo is shown in that attached drawing 1, microscopic appearance SEM photograph are shown in that attached drawing 2, the competing photo of transmission electricity are shown in attached drawing 3.It can be seen that appearance is bubble
The solid of foam shape, quality is very light, and SEM shows that microstructure is that graphite flake layer stacks, and TEM, which is shown on graphite flake layer, to be existed
It is a large amount of mesoporous, and mesoporous interconnection.
Embodiment 2
13.6g pentaerythrite is weighed in flask, 29.40g phosphoric acid is added, (vacuum degree 0.1MPa) is depressurized in stirring, add
Heat keeps the temperature 1.5h, obtains the thick pentaerythritol phosphate liquid of pale yellow transparent to 120 DEG C.Add in another round-bottomed flask
Enter 120mL ethyl alcohol and 16.38g melamine, 1.5h is sufficiently stirred, the pentaerythritol phosphate synthesized in upper step is poured into
In melamine equipped with alcohol dispersant, be heated to 80 DEG C, be stirred at reflux 6h, obtain white emulsion, rotary evaporation it is big
White solid is put in quartz boat by white solid, and under nitrogen atmosphere, the heating rate of 5 DEG C/min is warming up to 350 DEG C, is kept
0.5h is continued to be warming up to 900 DEG C with the heating rate of 5 DEG C/min, keeps 2h, be cooled to room temperature taking-up.Its microscopic appearance SEM is shown in
Attached drawing 4.It can be seen that SEM shows that microscopic appearance is graphite platelet structure, graphite flake layer is with a thickness of 300-400nm or so.
Embodiment 3
6.8g pentaerythrite is weighed in flask, 29.40g phosphoric acid is added, (vacuum degree 0.1MPa) is depressurized in stirring, add
Heat keeps the temperature 1.5h, obtains the thick pentaerythritol phosphate liquid of pale yellow transparent to 120 DEG C.Add in another round-bottomed flask
Enter 120mL ethyl alcohol and 16.38g melamine, 1.5h is sufficiently stirred, the pentaerythritol phosphate synthesized in upper step is poured into
In melamine equipped with alcohol dispersant, be heated to 80 DEG C, be stirred at reflux 6h, obtain white emulsion, rotary evaporation it is big
White solid is put in quartz boat by white solid, and under nitrogen atmosphere, the heating rate of 5 DEG C/min is warming up to 350 DEG C, is kept
0.5h is continued to be warming up to 1000 DEG C with the heating rate of 5 DEG C/min, keeps 2h, be cooled to room temperature taking-up.Its physical absorption curve
See that attached drawing 5, pore size distribution curve are shown in attached drawing 6. it can be seen that there are hysteresis loop in physical absorption curve, show to have mesoporous
In the presence of thus calculating specific surface area is 1717m2/g, is simulated to its pore-size distribution by DFT, there are two in aperture
The integrated distribution of pore diameter range, one is the micropore less than two nanometers, another is mesoporous for 3-8 nanometers.
Claims (8)
1. a kind of preparation method of carbon aerogels, it is characterised in that: contain N element in the carbon aerogels, while also containing different
One or more of prime element P, S, B, include the following steps,
(1) preparation of carbon aerogels precursor: polyalcohol and inorganic acid are stirred evenly and are heated and vacuumized that bring it about esterification anti-
It answers, the dispersion liquid containing amino-compound is added in gained reaction product end of reaction, and being uniformly mixed and heating again makes its hair
Reactant salt is generated, carbon aerogels precursor is obtained；
(2) preparation of carbon aerogels: carbon aerogels precursor obtained by step (1) is nitrogen atmosphere high temperature carbonization treatment, is obtained
Carbon aerogels.
2. the preparation method of carbon aerogels as described in claim 1, it is characterised in that: the quality of N element in the carbon aerogels
Content is 1%-7%, and total mass content of one or more of described heterogeneous element P, S, B are 1%-5%.
3. the preparation method of carbon aerogels as described in claim 1, it is characterised in that: the carbon aerogels are by porous graphite flake
Layer is crosslinked, and contains micropore, mesoporous and macroporous structure；The macropore is stacked by graphite flake layer, described mesoporous to be distributed in
On graphite flake layer, the micropore is present on the mesoporous wall of graphite flake layer.
4. the preparation method of carbon aerogels as claimed in claim 3, it is characterised in that: the total pore volume of the carbon aerogels is 1.5
-3 m3 g-1；The Micropore volume accounts for the 40%-90% of total pore volume, and macropore and mesoporous Kong Rong account for the 10%-60% of total pore volume.
5. the preparation method of carbon aerogels as described in claim 1, it is characterised in that: polyalcohol described in step (1) with it is inorganic
The ratio of the amount of the substance of acid is 2:1-1:8；The ratio of the amount of the substance of the inorganic acid and amino-compound is 5:1-1:5.
6. the preparation method of carbon aerogels as described in claim 1, it is characterised in that: solvent is water, methanol, second in step (1)
Alcohol, ethylene glycol or two kinds and two or more mixed liquors；The polyalcohol is pentaerythrite, xylitol, it is a kind of in sorbierite or
It is two or more；The inorganic acid is one or more kinds of in boric acid, phosphoric acid or sulfuric acid；The amino-compound is urea, three
It is poly cyanamid, cyanamide, one or more kinds of in amino acid；The solvent of dispersion liquid be one of methanol, ethyl alcohol or ethylene glycol or
Two kinds or more of mixed liquor.
7. the preparation method of carbon aerogels as described in claim 1, it is characterised in that: the item of esterification described in step (1)
Part is to react 0.5-5h at 70-200 DEG C；Vacuum degree is 0.03-0.2Mpa, and the salt-forming reaction condition is 30-150 DEG C of temperature
Lower reaction 2-24h.
8. the preparation method of carbon aerogels as described in claim 1, it is characterised in that: carbonization treatment condition described in step (2)
To be 2-10 DEG C/min with heating rate, from room temperature to 300-600 DEG C and 0.5-3h is kept, is again 2- with heating rate
10 DEG C/min increases temperature to 700-1100 DEG C, keeps this temperature 0.5-3h, is cooled to room temperature.
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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 |
| CN108394882B (en) * | 2018-03-08 | 2021-04-06 | 中国检验检疫科学研究院 | Ultra-light porous carbon material and preparation method thereof |
| 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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| WO2004009673A1 (en) * | 2002-07-22 | 2004-01-29 | Aspen Aerogels, Inc. | Polyimide aerogels, carbon aerogels, and metal carbide aerogels and methods of making same |
| CN102874796A (en) * | 2012-09-17 | 2013-01-16 | 中国科学院山西煤炭化学研究所 | Nitrogen mixed grapheme hydrogel or aerogel and preparation method thereof |
| 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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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN104245578A (en) * | 2012-03-09 | 2014-12-24 | 巴斯夫欧洲公司 | Aerogel based on doped graphene |
| EP2687483A1 (en) * | 2012-07-16 | 2014-01-22 | Basf Se | Graphene containing nitrogen and optionally iron and/or cobalt |
| CN102874796A (en) * | 2012-09-17 | 2013-01-16 | 中国科学院山西煤炭化学研究所 | Nitrogen mixed grapheme hydrogel or aerogel and preparation method thereof |
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