CN106185890B - A kind of preparation method of porous class graphene - Google Patents
A kind of preparation method of porous class graphene Download PDFInfo
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- CN106185890B CN106185890B CN201610516246.3A CN201610516246A CN106185890B CN 106185890 B CN106185890 B CN 106185890B CN 201610516246 A CN201610516246 A CN 201610516246A CN 106185890 B CN106185890 B CN 106185890B
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Abstract
The invention discloses a kind of preparation methods of porous class graphene, it is characterised in that: using coal tar pitch as raw material, using ammonium class inorganic salts as pore creating material, under inert atmosphere, 800~1100 DEG C are heated to, porous class grapheme material is made after drying in a vacuum drying oven in washing by soaking after cooling.Compared with prior art, the features such as present invention has raw material cheap and easy to get, and preparation method is simple, does not introduce or generate the substance of pollution environment, environmentally protective, high financial profit.Porous class grapheme material prepared by the present invention, specific surface area is high, and even aperture distribution has a wide range of applications in fields such as catalysis, absorption, supercapacitors.
Description
Technical field
The present invention relates to a kind of preparation methods of porous class graphene, belong to technical field of nanometer material preparation.
Background technique
Graphene is a kind of New Two Dimensional nano material being just found for 2004, due to its excellent optics, electricity, power
And biology performance, and get more and more people's extensive concerning.However graphene itself is two-dimensional structure, ion and electronics are vertical
In the diffusion on graphene film field direction by great limitation, to reduce its hair as battery conductive agent performance
It waves, it is therefore necessary to develop a kind of novel graphene-structured, without limitation on ion on perpendicular to graphene sheet layer direction
Transmission.
In view of the above problems, researcher prepares the graphite material of porous structure using various methods.
A kind of graphene and preparation method thereof with porous structure is disclosed in Chinese patent CN102115069A, is passed through
The metallic catalysts such as carrier loaded Fe, Co are prepared in certain temperature range with the chemical deposition of hydrocarbon gas progress gas phase
The graphene of porous structure.
Chinese patent CN104752703A discloses a kind of porous class graphene and preparation method thereof, utilizes graphite, oxidation
Graphite etc. is used as original carbon material, directs it arrangement using the methods of gas-liquid interface self assembly, magnetization arrangement, final synthesis is more
The graphene of pore structure.
Chinese patent CN104098091A discloses a kind of method for preparing supercapacitor porous graphene material, with
Coal tar pitch is carbon source, and nanometer calcium carbonate is template, and potassium hydroxide is activator, is heated under normal pressure or condition of negative pressure in tube furnace
Activation, directly obtains supercapacitor porous graphene material.From the point of view of the prior art retrieved, current porous class graphite
The preparation method of alkene, not only complex process, but also use metallic element and the reagents such as the strong acid that can cause environmental pollution, at
This height, deficiency in economic performance are unfavorable for commercialized application.
Therefore, one kind is using coal tar pitch as raw material, using ammonium class inorganic salts as pore creating material, by simply heating preparation with more
The grapheme material of pore structure is suggested, and this method simple process, low in raw material price is from a wealth of sources, before having good market
Scape.
Summary of the invention
The object of the present invention is to provide a kind of preparation method is simple, raw material sources are extensive, at low cost, application prospect it is good and
The environmentally protective method that porous class graphene is prepared as raw material using coal tar pitch.
A kind of preparation method of porous class graphene, it is characterised in that be mainly prepared by the following steps:
(1) raw material mixing and pretreatment: the ratio that coal tar pitch and ammonium class inorganic salts are 1:5~20 in mass ratio is mixed,
And the powder being mixed to get is put into 180~200 DEG C of environment oxidation 12~for 24 hours；
(2) powder made from step (1) is packed into porcelain boat, and is put into tube furnace, in an inert atmosphere with 4~6 DEG C/
Min is warming up to 300 DEG C, keeps 1~2h, then be warming up to 500 DEG C with 4~6 DEG C/min, 1~2h is kept, finally with 4~6 DEG C/min
800~1100 DEG C are warming up to, 1~2h is kept, is cooled to room temperature discharging later；
(3) porous class grapheme material is made by product washing by soaking made from step (2), and after drying.
The coal tar pitch and ammonium class inorganic salts are sufficiently mixed uniformly in ball milling instrument.
In actual use: in above-mentioned steps (3), product made from step (2) is impregnated with deionized water, is washed 3-4 times,
It is subsequently placed in 10~12h in the vacuum oven that temperature is 80~100 DEG C, finally obtains porous graphene material.
The coal tar pitch is medium temperature coal pitch.
The ammonium class inorganic salts are at least one of ammonium sulfate or ammonium phosphate.
The inert gas is one of nitrogen or argon gas.
Compared with prior art, the invention has the following advantages:
One, raw material sources are extensive, cheap, have wide commercial promise；
Two, preparation process is simple, the principle to be reduced foaming using ammonium class inorganic salts, prepares porous structure by a step heating
Class graphene；
Three, the features such as using corrosive reagent, avoiding environmental pollution and the wasting of resources is not needed.
The grapheme material as made from this method, specific surface area is high, even aperture distribution, in catalysis, absorption, super electricity
The fields such as container have a wide range of applications.
Detailed description of the invention
Fig. 1~5 are the transmission electron microscope photos of porous class graphene produced by the present invention.
Specific embodiment
A kind of embodiment 1: preparation method of porous class graphene, it is characterised in that be prepared by the following method: by medium temperature
Coal tar pitch and ammonium sulfate or ammonium phosphate are that the ratio of 1:5 is sufficiently mixed uniformly in ball milling instrument, and will be mixed to get in mass ratio
Powder be put into the baking oven of 200 DEG C of environment and aoxidize for 24 hours, powder obtained will be packed into porcelain boat after oxidation later, and be put into tubular type
In furnace, 300 DEG C are warming up to 5 DEG C/min in nitrogen atmosphere, 1.9h is kept, then be warming up to 500 DEG C with 4.8 DEG C/min, keeps
2h is finally warming up to 1070 DEG C with 5 DEG C/min, keeps 1h, is cooled to room temperature discharging later, finally impregnates in deionized water,
And wash 3 times, it is subsequently placed in 10.8h in the vacuum oven that temperature is 92 DEG C, porous class grapheme material is made after dry.
A kind of embodiment 2: preparation method of porous class graphene, it is characterised in that be prepared by the following method: by medium temperature
Coal tar pitch and ammonium sulfate or ammonium phosphate are that the ratio of 1:7 is sufficiently mixed uniformly in ball milling instrument, and will be mixed to get in mass ratio
Powder be put into the baking oven of 198 DEG C of environment and aoxidize 23h, powder obtained will be packed into porcelain boat after oxidation later, and be put into tubular type
In furnace, 300 DEG C are warming up to 4.2 DEG C/min in nitrogen atmosphere, 1.8h is kept, then be warming up to 500 DEG C with 5 DEG C/min, keeps
1.4h is finally warming up to 1100 DEG C with 5.2 DEG C/min, keeps 1.2h, is cooled to room temperature discharging later, finally in deionized water
It impregnates, and washs 3 times, be subsequently placed in 11h in the vacuum oven that temperature is 80 DEG C, porous class graphene material is made after dry
Material.
A kind of embodiment 3: preparation method of porous class graphene, it is characterised in that be prepared by the following method: by medium temperature
Coal tar pitch and ammonium sulfate or ammonium phosphate are that the ratio of 1:9 is sufficiently mixed uniformly in ball milling instrument, and will be mixed to get in mass ratio
Powder be put into the baking oven of 196 DEG C of environment and aoxidize 22h, powder obtained will be packed into porcelain boat after oxidation later, and be put into tubular type
In furnace, 300 DEG C are warming up to 4.4 DEG C/min in nitrogen atmosphere, 1h is kept, then be warming up to 500 DEG C with 5.2 DEG C/min, keeps
1.3h is finally warming up to 800 DEG C with 4.8 DEG C/min, keeps 1.8h, is cooled to room temperature discharging later, finally in deionized water
It impregnates, and washs 4 times, be subsequently placed in 11.2h in the vacuum oven that temperature is 82 DEG C, porous class graphene material is made after dry
Material.
A kind of embodiment 4: preparation method of porous class graphene, it is characterised in that be prepared by the following method: by medium temperature
Coal tar pitch and ammonium sulfate or ammonium phosphate are that the ratio of 1:11 is sufficiently mixed uniformly in ball milling instrument, and will be mixed to get in mass ratio
Powder be put into the baking oven of 194 DEG C of environment and aoxidize 12h, powder obtained will be packed into porcelain boat after oxidation later, and be put into tubular type
In furnace, 300 DEG C are warming up to 4.6 DEG C/min in nitrogen atmosphere, 1.1h is kept, then be warming up to 500 DEG C with 5.4 DEG C/min, protects
1h is held, is finally warming up to 830 DEG C with 4.6 DEG C/min, 1.7h is kept, is cooled to room temperature discharging later, finally in deionized water
It impregnates, and washs 4 times, be subsequently placed in 10.6h in the vacuum oven that temperature is 84 DEG C, porous class graphene material is made after dry
Material.
A kind of embodiment 5: preparation method of porous class graphene, it is characterised in that be prepared by the following method: by medium temperature
Coal tar pitch and ammonium sulfate or ammonium phosphate are that the ratio of 1:13 is sufficiently mixed uniformly in ball milling instrument, and will be mixed to get in mass ratio
Powder be put into the baking oven of 192 DEG C of environment and aoxidize 13h, powder obtained will be packed into porcelain boat after oxidation later, and be put into tubular type
In furnace, 300 DEG C are warming up to 5.8 DEG C/min in nitrogen atmosphere, 1.2h is kept, then be warming up to 500 DEG C with 5.6 DEG C/min, protects
1.2h is held, is finally warming up to 860 DEG C with 4.2 DEG C/min, 1.6h is kept, discharging is cooled to room temperature later, finally in deionized water
Middle immersion, and wash 3 times, it is subsequently placed in 10.4h in the vacuum oven that temperature is 94 DEG C, porous class graphene is made after dry
Material.
A kind of embodiment 6: preparation method of porous class graphene, it is characterised in that be prepared by the following method: by medium temperature
Coal tar pitch and ammonium sulfate or ammonium phosphate are that the ratio of 1:15 is sufficiently mixed uniformly in ball milling instrument, and will be mixed to get in mass ratio
Powder be put into the baking oven of 190 DEG C of environment and aoxidize 14h, powder obtained will be packed into porcelain boat after oxidation later, and be put into tubular type
In furnace, 300 DEG C are warming up to 6 DEG C/min in nitrogen atmosphere, 1.3h is kept, then be warming up to 500 DEG C with 5.8 DEG C/min, keeps
1.5h is finally warming up to 1040 DEG C with 4 DEG C/min, keeps 1.5h, is cooled to room temperature discharging later, finally soaks in deionized water
Bubble, and wash 3 times, it is subsequently placed in 10.2h in the vacuum oven that temperature is 96 DEG C, porous class graphene material is made after dry
Material.
A kind of embodiment 7: preparation method of porous class graphene, it is characterised in that be prepared by the following method: by medium temperature
Coal tar pitch and ammonium sulfate or ammonium phosphate are that the ratio of 1:17 is sufficiently mixed uniformly in ball milling instrument, and will be mixed to get in mass ratio
Powder be put into the baking oven of 188 DEG C of environment and aoxidize 16h, powder obtained will be packed into porcelain boat after oxidation later, and be put into tubular type
In furnace, 300 DEG C are warming up to 4 DEG C/min in argon atmosphere, 2h is kept, then be warming up to 500 DEG C with 6 DEG C/min, keeps 1.1h,
890 DEG C finally are warming up to 5.4 DEG C/min, 1.9h is kept, is cooled to room temperature discharging later, finally impregnates in deionized water,
And wash 3 times, it is subsequently placed in 10h in the vacuum oven that temperature is 86 DEG C, porous class grapheme material is made after dry.
A kind of embodiment 8: preparation method of porous class graphene, it is characterised in that be prepared by the following method: by medium temperature
Coal tar pitch and ammonium sulfate or ammonium phosphate are that the ratio of 1:19 is sufficiently mixed uniformly in ball milling instrument, and will be mixed to get in mass ratio
Powder be put into the baking oven of 186 DEG C of environment and aoxidize 21h, powder obtained will be packed into porcelain boat after oxidation later, and be put into tubular type
In furnace, 300 DEG C are warming up to 5.4 DEG C/min in argon atmosphere, 1.7h is kept, then be warming up to 500 DEG C with 4.4 DEG C/min, protects
1.6h is held, is finally warming up to 920 DEG C with 4.4 DEG C/min, 2h is kept, is cooled to room temperature discharging later, finally in deionized water
It impregnates, and washs 4 times, be subsequently placed in 11.4h in the vacuum oven that temperature is 88 DEG C, porous class graphene material is made after dry
Material.
A kind of embodiment 9: preparation method of porous class graphene, it is characterised in that be prepared by the following method: by medium temperature
Coal tar pitch and ammonium sulfate or ammonium phosphate are that the ratio of 1:20 is sufficiently mixed uniformly in ball milling instrument, and will be mixed to get in mass ratio
Powder be put into the baking oven of 184 DEG C of environment and aoxidize 20h, powder obtained will be packed into porcelain boat after oxidation later, and be put into tubular type
In furnace, 300 DEG C are warming up to 5.2 DEG C/min in argon atmosphere, 1.6h is kept, then be warming up to 500 DEG C with 4.6 DEG C/min, protects
1.7h is held, is finally warming up to 1010 DEG C with 6 DEG C/min, 1.1h is kept, is cooled to room temperature discharging later, finally in deionized water
It impregnates, and washs 4 times, be subsequently placed in 11.6h in vacuum oven at a temperature of 90 °C, porous class graphene material is made after dry
Material.
A kind of embodiment 10: preparation method of porous class graphene, it is characterised in that be prepared by the following method: by medium temperature
Coal tar pitch and ammonium sulfate or ammonium phosphate are that the ratio of 1:7 is sufficiently mixed uniformly in ball milling instrument, and will be mixed to get in mass ratio
Powder be put into the baking oven of 182 DEG C of environment and aoxidize 19h, powder obtained will be packed into porcelain boat after oxidation later, and be put into tubular type
In furnace, 300 DEG C are warming up to 5 DEG C/min in argon atmosphere, 1.4h is kept, then be warming up to 500 DEG C with 4.2 DEG C/min, keeps
1.9h is finally warming up to 950 DEG C with 5.8 DEG C/min, keeps 1.3h, is cooled to room temperature discharging later, finally in deionized water
It impregnates, and washs 4 times, be subsequently placed in 11.8h in the vacuum oven that temperature is 98 DEG C, porous class graphene material is made after dry
Material.
A kind of embodiment 11: preparation method of porous class graphene, it is characterised in that be prepared by the following method: by medium temperature
Coal tar pitch and ammonium sulfate or ammonium phosphate are that the ratio of 1:11 is sufficiently mixed uniformly in ball milling instrument, and will be mixed to get in mass ratio
Powder be put into the baking oven of 180 DEG C of environment and aoxidize 18h, powder obtained will be packed into porcelain boat after oxidation later, and be put into tubular type
In furnace, 300 DEG C are warming up to 4.8 DEG C/min in argon atmosphere, 1.5h is kept, then be warming up to 500 DEG C with 4 DEG C/min, keeps
1.8h is finally warming up to 980 DEG C with 5.6 DEG C/min, keeps 1.4h, is cooled to room temperature discharging later, finally in deionized water
It impregnates, and washs 3 times, be subsequently placed in 12h in the vacuum oven that temperature is 100 DEG C, porous class graphene material is made after dry
Material.
Claims (9)
1. a kind of preparation method of porous class graphene, it is characterised in that be mainly prepared by the following steps:
(1) raw material mixing and pretreatment: the ratio that coal tar pitch and ammonium class inorganic salts are 1:5~20 in mass ratio is mixed, and will
The powder being mixed to get is put into 180~200 DEG C of environment oxidation 12~for 24 hours；
(2) powder made from step (1) is packed into porcelain boat, and be put into tube furnace, in an inert atmosphere with 4~6 DEG C/min liter
Temperature keeps 1~2h to 300 DEG C, then is warming up to 500 DEG C with 4~6 DEG C/min, keeps 1~2h, finally with 4~6 DEG C/min heating
To 800 DEG C, 1~2h is kept, later cooling discharging；
(3) porous class grapheme material is made by product washing by soaking made from step (2), and after drying.
2. a kind of preparation method of porous class graphene according to claim 1, it is characterised in that: in above-mentioned (3) step,
After washing by soaking, it is placed in 10~12h in the vacuum oven that temperature is 80~100 DEG C, obtains porous graphene material later.
3. a kind of preparation method of porous class graphene according to claim 1 or 2, it is characterised in that: the coal tar pitch
For medium temperature coal pitch.
4. a kind of preparation method of porous class graphene according to claim 1 or 2, it is characterised in that: the ammonium class without
Machine salt is at least one of ammonium sulfate or ammonium phosphate.
5. a kind of preparation method of porous class graphene according to claim 3, it is characterised in that: the ammonium class inorganic salts
For at least one of ammonium sulfate or ammonium phosphate.
6. a kind of preparation method of porous class graphene according to claim 1 or 2, it is characterised in that: coal in step (1)
Pitch and ammonium class inorganic salts are sufficiently mixed uniformly in ball milling instrument.
7. a kind of preparation method of porous class graphene according to claim 3, it is characterised in that: coal drips in step (1)
It is green to be sufficiently mixed in ball milling instrument uniformly with ammonium class inorganic salts.
8. a kind of preparation method of porous class graphene according to claim 1 or 2, it is characterised in that: the indifferent gas
Body is one of nitrogen or argon gas.
9. a kind of preparation method of porous class graphene according to claim 3, it is characterised in that: the inert gas is
One of nitrogen or argon gas.
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| CN108033440B (en) * | 2018-01-16 | 2021-07-13 | 上海理工大学 | Preparation method of porous folded graphene with high specific surface area |
| CN111377445B (en) * | 2018-12-29 | 2022-09-09 | 中国石油化工股份有限公司 | Petroleum coke-based active carbon material and preparation method thereof |
| CN111377444B (en) * | 2018-12-29 | 2022-09-09 | 中国石油化工股份有限公司 | Petroleum coke-based activated carbon and preparation method thereof |
| CN110265646B (en) * | 2019-06-25 | 2022-09-16 | 西南大学 | Nitrogen-doped graphene-like activated carbon material and preparation method and application thereof |
| CN115417401A (en) * | 2022-05-12 | 2022-12-02 | 太原理工大学 | Method for preparing graphene by recoverable low-temperature molten salt |
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| CN103466604A (en) * | 2013-08-13 | 2013-12-25 | 华东理工大学 | Preparation method of porous graphene |
| CN103787327B (en) * | 2014-03-06 | 2015-11-18 | 安徽工业大学 | The ultracapacitor one-step preppn process of hollow sphere porous graphene |
| CN105329883A (en) * | 2015-10-14 | 2016-02-17 | 南京邮电大学 | Porous graphene preparation method |
| CN105480971B (en) * | 2016-01-29 | 2017-07-04 | 福州大学 | A kind of preparation method of asphaltic base three-dimensional meso-hole grapheme material |
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