CN106185890A - 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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- CN106185890A CN106185890A CN201610516246.3A CN201610516246A CN106185890A CN 106185890 A CN106185890 A CN 106185890A CN 201610516246 A CN201610516246 A CN 201610516246A CN 106185890 A CN106185890 A CN 106185890A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
Abstract
The invention discloses the preparation method of a kind of porous class Graphene, it is characterised in that: with coal tar pitch as raw material, with ammonium class inorganic salt as pore creating material, under inert atmosphere, it is heated to 800～1100 DEG C, washing by soaking after cooling, prepare porous class grapheme material after drying in vacuum drying oven.Compared with prior art, the present invention has cheaper starting materials and is easy to get, and preparation method is simple, does not introduces or produce the material polluting environment, environmental protection, the features such as economic benefit is high.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, ultracapacitors.
Description
Technical field
The present invention relates to the preparation method of a kind of porous class Graphene, belong to technical field of nanometer material preparation.
Background technology
Graphene is a kind of New Two Dimensional nano material being just found for 2004, due to the optics of its excellence, electricity, power
Learn and biology performance, and get more and more people's extensive concerning.But Graphene itself is two-dimensional structure, ion and electronics are vertically
Great restriction has been suffered in diffusion on graphene film field direction, thus reduces its sending out as battery conductive agent performance
Wave, it is therefore necessary to develop a kind of novel graphene-structured, be perpendicular on graphene sheet layer direction without limitation on ion
Transmission.
For problem above, researcher uses various methods to prepare the graphite material of loose structure.
Chinese patent CN102115069A discloses a kind of Graphene with loose structure and preparation method thereof, passes through
The metallic catalysts such as carrier loaded Fe, Co, in certain temperature range, and hydrocarbon gas carries out the chemical deposition of gas phase and is prepared for
The Graphene of loose structure.
Chinese patent CN104752703A discloses a kind of porous class Graphene and preparation method thereof, utilizes graphite, oxidation
Graphite etc., as original material with carbon element, utilize the method such as gas-liquid interface self assembly, magnetization arrangement to direct it arrangement, and final synthesis is many
The Graphene of pore structure.
Chinese patent CN104098091A discloses a kind of method preparing ultracapacitor porous graphene material, with
Coal tar pitch is carbon source, and nano-calcium carbonate is template, and potassium hydroxide is activator, heats in tube furnace under normal pressure or condition of negative pressure
Activation, directly obtains ultracapacitor 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 reagent such as the strong acid of environment can be become
This height, deficiency in economic performance, it is unfavorable for business-like application.
Therefore, a kind of with coal tar pitch as raw material, with ammonium class inorganic salt as pore creating material, have many by simply adding hot preparation
The grapheme material of pore structure is suggested, and this method technique is simple, and low in raw material price, wide material sources, before having good market
Scape.
Summary of the invention
It is an object of the invention to provide a kind of preparation method simple, raw material sources are extensive, low cost, application prospect good and
The method preparing porous class Graphene for raw material with coal tar pitch of environmental protection.
The preparation method of a kind of porous class Graphene, it is characterised in that mainly prepared by following steps:
(1) raw material mixing and pretreatment: be the ratio mixing of 1:5～20 in mass ratio by coal tar pitch and ammonium class inorganic salt,
And the powder being mixed to get is put into oxidation 12～24h in 180～200 DEG C of environment；
(2) powder that step (1) prepares is loaded porcelain boat, and puts in tube furnace, in an inert atmosphere with 4～6 DEG C/
Min is warming up to 300 DEG C, keeps 1～2h, then is warming up to 500 DEG C with 4～6 DEG C/min, keeps 1～2h, finally with 4～6 DEG C/min
It is warming up to 800～1100 DEG C, keeps 1～2h, be cooled to room temperature discharging afterwards；
(3) the product washing by soaking that step (2) is prepared, and prepare porous class grapheme material after drying.
Described coal tar pitch and ammonium class inorganic salt are sufficiently mixed uniformly in ball milling instrument.
Time actually used: in above-mentioned steps (3), product with deionized water step (2) prepared is soaked, and washs 3-4 time,
It is subsequently placed in the vacuum drying oven that temperature is 80～100 DEG C 10～12h, finally obtains porous graphene material.
Described coal tar pitch is medium temperature coal pitch.
Described ammonium class inorganic salt is at least one in ammonium sulfate or ammonium phosphate.
Described noble gas is the one in nitrogen or argon.
Compared with prior art, the method have the advantages that
One, raw material sources are extensive, cheap, have wide commercial promise；
Two, preparation process is simple, and the principle utilizing ammonium class inorganic salt to reduce foaming adds hot preparation loose structure by a step
Class Graphene；
Three, need not to use corrosive reagent, it is to avoid the feature such as environmental pollution and the wasting of resources.
The grapheme material prepared by this method, specific surface area is high, even aperture distribution, at catalysis, absorption, super electricity
The fields such as container have a wide range of applications.
Accompanying drawing explanation
Fig. 1～5 is the transmission electron microscope photo of the porous class Graphene that the present invention prepares.
Detailed description of the invention
Embodiment 1: the preparation method of a kind of porous class Graphene, it is characterised in that be prepared by the following method: by middle 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 in mass ratio, and will be mixed to get
Powder put into the baking oven of 200 DEG C of environment aoxidize 24h, the powder loading porcelain boat that will prepare after oxidation afterwards, and put into tubular type
In stove, in nitrogen atmosphere, it is warming up to 300 DEG C with 5 DEG C/min, keeps 1.9h, then be warming up to 500 DEG C with 4.8 DEG C/min, keep
2h, is finally warming up to 1070 DEG C with 5 DEG C/min, keeps 1h, is cooled to room temperature discharging afterwards, soaks the most in deionized water,
And wash 3 times, it is subsequently placed in 10.8h in the vacuum drying oven that temperature is 92 DEG C, dried prepared porous class grapheme material.
Embodiment 2: the preparation method of a kind of porous class Graphene, it is characterised in that be prepared by the following method: by middle 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 in mass ratio, and will be mixed to get
Powder put into the baking oven of 198 DEG C of environment aoxidize 23h, the powder loading porcelain boat that will prepare after oxidation afterwards, and put into tubular type
In stove, in nitrogen atmosphere, it is warming up to 300 DEG C with 4.2 DEG C/min, keeps 1.8h, then be warming up to 500 DEG C with 5 DEG C/min, keep
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 afterwards, the most in deionized water
Soak, and wash 3 times, be subsequently placed in 11h in the vacuum drying oven that temperature is 80 DEG C, dried prepared porous class Graphene material
Material.
Embodiment 3: the preparation method of a kind of porous class Graphene, it is characterised in that be prepared by the following method: by middle 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 in mass ratio, and will be mixed to get
Powder put into the baking oven of 196 DEG C of environment aoxidize 22h, the powder loading porcelain boat that will prepare after oxidation afterwards, and put into tubular type
In stove, in nitrogen atmosphere, it is warming up to 300 DEG C with 4.4 DEG C/min, keeps 1h, then be warming up to 500 DEG C with 5.2 DEG C/min, keep
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 afterwards, the most in deionized water
Soak, and wash 4 times, be subsequently placed in 11.2h in the vacuum drying oven that temperature is 82 DEG C, dried prepared porous class Graphene material
Material.
Embodiment 4: the preparation method of a kind of porous class Graphene, it is characterised in that be prepared by the following method: by middle 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 in mass ratio, and will be mixed to get
Powder put into the baking oven of 194 DEG C of environment aoxidize 12h, the powder loading porcelain boat that will prepare after oxidation afterwards, and put into tubular type
In stove, in nitrogen atmosphere, it is warming up to 300 DEG C with 4.6 DEG C/min, keeps 1.1h, then be warming up to 500 DEG C with 5.4 DEG C/min, protect
Hold 1h, be finally warming up to 830 DEG C with 4.6 DEG C/min, keep 1.7h, be cooled to room temperature discharging afterwards, the most in deionized water
Soak, and wash 4 times, be subsequently placed in 10.6h in the vacuum drying oven that temperature is 84 DEG C, dried prepared porous class Graphene material
Material.
Embodiment 5: the preparation method of a kind of porous class Graphene, it is characterised in that be prepared by the following method: by middle 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 in mass ratio, and will be mixed to get
Powder put into the baking oven of 192 DEG C of environment aoxidize 13h, the powder loading porcelain boat that will prepare after oxidation afterwards, and put into tubular type
In stove, in nitrogen atmosphere, it is warming up to 300 DEG C with 5.8 DEG C/min, keeps 1.2h, then be warming up to 500 DEG C with 5.6 DEG C/min, protect
Hold 1.2h, be finally warming up to 860 DEG C with 4.2 DEG C/min, keep 1.6h, be cooled to room temperature discharging afterwards, finally at deionized water
Middle immersion, and wash 3 times, it is subsequently placed in 10.4h in the vacuum drying oven that temperature is 94 DEG C, dried prepared porous class Graphene
Material.
Embodiment 6: the preparation method of a kind of porous class Graphene, it is characterised in that be prepared by the following method: by middle 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 in mass ratio, and will be mixed to get
Powder put into the baking oven of 190 DEG C of environment aoxidize 14h, the powder loading porcelain boat that will prepare after oxidation afterwards, and put into tubular type
In stove, in nitrogen atmosphere, it is warming up to 300 DEG C with 6 DEG C/min, keeps 1.3h, then be warming up to 500 DEG C with 5.8 DEG C/min, keep
1.5h, is finally warming up to 1040 DEG C with 4 DEG C/min, keeps 1.5h, is cooled to room temperature discharging afterwards, soaks the most in deionized water
Bubble, and wash 3 times, it is subsequently placed in 10.2h in the vacuum drying oven that temperature is 96 DEG C, dried prepared porous class Graphene material
Material.
Embodiment 7: the preparation method of a kind of porous class Graphene, it is characterised in that be prepared by the following method: by middle 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 in mass ratio, and will be mixed to get
Powder put into the baking oven of 188 DEG C of environment aoxidize 16h, the powder loading porcelain boat that will prepare after oxidation afterwards, and put into tubular type
In stove, in argon gas atmosphere, it is warming up to 300 DEG C with 4 DEG C/min, keeps 2h, then be warming up to 500 DEG C with 6 DEG C/min, keep 1.1h,
Finally it is warming up to 890 DEG C with 5.4 DEG C/min, keeps 1.9h, be cooled to room temperature discharging afterwards, soak the most in deionized water,
And wash 3 times, it is subsequently placed in 10h in the vacuum drying oven that temperature is 86 DEG C, dried prepared porous class grapheme material.
Embodiment 8: the preparation method of a kind of porous class Graphene, it is characterised in that be prepared by the following method: by middle 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 in mass ratio, and will be mixed to get
Powder put into the baking oven of 186 DEG C of environment aoxidize 21h, the powder loading porcelain boat that will prepare after oxidation afterwards, and put into tubular type
In stove, in argon gas atmosphere, it is warming up to 300 DEG C with 5.4 DEG C/min, keeps 1.7h, then be warming up to 500 DEG C with 4.4 DEG C/min, protect
Hold 1.6h, be finally warming up to 920 DEG C with 4.4 DEG C/min, keep 2h, be cooled to room temperature discharging afterwards, the most in deionized water
Soak, and wash 4 times, be subsequently placed in 11.4h in the vacuum drying oven that temperature is 88 DEG C, dried prepared porous class Graphene material
Material.
Embodiment 9: the preparation method of a kind of porous class Graphene, it is characterised in that be prepared by the following method: by middle 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 in mass ratio, and will be mixed to get
Powder put into the baking oven of 184 DEG C of environment aoxidize 20h, the powder loading porcelain boat that will prepare after oxidation afterwards, and put into tubular type
In stove, in argon gas atmosphere, it is warming up to 300 DEG C with 5.2 DEG C/min, keeps 1.6h, then be warming up to 500 DEG C with 4.6 DEG C/min, protect
Hold 1.7h, be finally warming up to 1010 DEG C with 6 DEG C/min, keep 1.1h, be cooled to room temperature discharging afterwards, the most in deionized water
Soak, and wash 4 times, be subsequently placed in 11.6h in the vacuum drying oven that temperature is 90 DEG C, dried prepared porous class Graphene material
Material.
Embodiment 10: the preparation method of a kind of porous class Graphene, it is characterised in that be prepared by the following method: by middle 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 in mass ratio, and will be mixed to get
Powder put into the baking oven of 182 DEG C of environment aoxidize 19h, the powder loading porcelain boat that will prepare after oxidation afterwards, and put into tubular type
In stove, in argon gas atmosphere, it is warming up to 300 DEG C with 5 DEG C/min, keeps 1.4h, then be warming up to 500 DEG C with 4.2 DEG C/min, keep
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 afterwards, the most in deionized water
Soak, and wash 4 times, be subsequently placed in 11.8h in the vacuum drying oven that temperature is 98 DEG C, dried prepared porous class Graphene material
Material.
Embodiment 11: the preparation method of a kind of porous class Graphene, it is characterised in that be prepared by the following method: by middle 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 in mass ratio, and will be mixed to get
Powder put into the baking oven of 180 DEG C of environment aoxidize 18h, the powder loading porcelain boat that will prepare after oxidation afterwards, and put into tubular type
In stove, in argon gas atmosphere, it is warming up to 300 DEG C with 4.8 DEG C/min, keeps 1.5h, then be warming up to 500 DEG C with 4 DEG C/min, keep
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 afterwards, the most in deionized water
Soak, and wash 3 times, be subsequently placed in 12h in the vacuum drying oven that temperature is 100 DEG C, dried prepared porous class Graphene material
Material.
Claims (9)
1. the preparation method of a porous class Graphene, it is characterised in that mainly prepared by following steps:
(1) raw material mixing and pretreatment: be the ratio mixing of 1:5～20 in mass ratio by coal tar pitch and ammonium class inorganic salt, and will
The powder being mixed to get is put into and is aoxidized 12～24h in 180～200 DEG C of environment；
(2) powder that step (1) prepares is loaded porcelain boat, and put in tube furnace, in an inert atmosphere with 4～6 DEG C/min liter
Temperature, to 300 DEG C, keeps 1～2h, then is warming up to 500 DEG C with 4～6 DEG C/min, keeps 1～2h, finally heats up with 4～6 DEG C/min
To 800～1100 DEG C, keep 1～2h, cooling discharging afterwards；
(3) the product washing by soaking that step (2) is prepared, and prepare porous class grapheme material after drying.
The preparation method of a kind of porous class Graphene the most according to claim 1, it is characterised in that: in above-mentioned (3) step,
After washing by soaking, it is placed in the vacuum drying oven that temperature is 80～100 DEG C 10～12h, obtains porous graphene material afterwards.
The preparation method of a kind of porous class Graphene the most according to claim 1 and 2, it is characterised in that: described coal tar pitch
For medium temperature coal pitch.
The preparation method of a kind of porous class Graphene the most according to claim 1 and 2, it is characterised in that: described ammonium class without
Machine salt is at least one in ammonium sulfate or ammonium phosphate.
The preparation method of a kind of porous class Graphene the most according to claim 3, it is characterised in that: described ammonium class inorganic salt
For at least one in ammonium sulfate or ammonium phosphate.
The preparation method of a kind of porous class Graphene the most according to claim 1 and 2, it is characterised in that: coal in step (1)
Colophonium and ammonium class inorganic salt are sufficiently mixed uniformly in ball milling instrument.
The preparation method of a kind of porous class Graphene the most according to claim 3, it is characterised in that: coal drip in step (1)
Blue or green and ammonium class inorganic salt is sufficiently mixed uniformly in ball milling instrument.
The preparation method of a kind of porous class Graphene the most according to claim 1 and 2, it is characterised in that: described indifferent gas
Body is the one in nitrogen or argon.
The preparation method of a kind of porous class Graphene the most according to claim 3, it is characterised in that: described noble gas is
One in nitrogen or argon.
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Cited By (5)
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| CN108033440A (en) * | 2018-01-16 | 2018-05-15 | 上海理工大学 | A kind of preparation method of high specific surface area porous fold graphene |
| CN110265646A (en) * | 2019-06-25 | 2019-09-20 | 西南大学 | A kind of N doping class graphene active carbon material and its preparation method and application |
| CN111377444A (en) * | 2018-12-29 | 2020-07-07 | 中国石油化工股份有限公司 | Petroleum coke-based activated carbon and preparation method thereof |
| CN111377445A (en) * | 2018-12-29 | 2020-07-07 | 中国石油化工股份有限公司 | Petroleum coke-based active carbon material and preparation method 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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| CN105329883A (en) * | 2015-10-14 | 2016-02-17 | 南京邮电大学 | Porous graphene preparation method |
| CN105480971A (en) * | 2016-01-29 | 2016-04-13 | 福州大学 | Preparation method of asphalt-based three-dimensional mesoporous graphene material |
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| CN103787327A (en) * | 2014-03-06 | 2014-05-14 | 安徽工业大学 | One-step preparation method of hollow spherical porous graphite for supercapacitor |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108033440A (en) * | 2018-01-16 | 2018-05-15 | 上海理工大学 | A kind of preparation method of high specific surface area porous fold graphene |
| CN111377444A (en) * | 2018-12-29 | 2020-07-07 | 中国石油化工股份有限公司 | Petroleum coke-based activated carbon and preparation method thereof |
| CN111377445A (en) * | 2018-12-29 | 2020-07-07 | 中国石油化工股份有限公司 | Petroleum coke-based active carbon material and preparation method thereof |
| 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 |
| CN110265646A (en) * | 2019-06-25 | 2019-09-20 | 西南大学 | A kind of N doping class graphene active carbon material and its preparation method and application |
| 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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