CN103387223A - Preparation method of graphite - Google Patents
Preparation method of graphite Download PDFInfo
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- CN103387223A CN103387223A CN201210137319XA CN201210137319A CN103387223A CN 103387223 A CN103387223 A CN 103387223A CN 201210137319X A CN201210137319X A CN 201210137319XA CN 201210137319 A CN201210137319 A CN 201210137319A CN 103387223 A CN103387223 A CN 103387223A
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Abstract
The invention provides a preparation method of graphite. The method comprises the following steps: carrying out high temperature reduction on graphite oxide under protection of inert gas at 800-1200 DEG C for 10-60 s; transferring the high temperature reduction products to liquid nitrogen, and cooling for 3-30 s; and after cooling, collecting a black powder namely the prepared graphite. In the method, huge temperature difference between high temperature reduction and liquid nitrogen refrigeration makes the graphite wrinkle more easily, thereby effectively avoiding agglomeration among sheet layers of the graphite. The graphite prepared by the method provided by the invention has a high specific surface area reaching 700-1500 m<2>/g. In addition, the method has simple process and short reaction time.
Description
Technical field
The present invention relates to the synthetic field of material, particularly relate to a kind of method for preparing Graphene.
Background technology
Graphene is a kind of Two-dimensional Carbon atomic crystal that the strong K of the peace moral of Univ Manchester UK in 2004 sea nurse (Andre K.Geim) etc. is found, is the carbon material as thin as a wafer of single or multiple lift.Single-layer graphene is due to its large specific surface area, good conduction, heat conductivility and low thermal expansivity and be considered to desirable material, as have: 1, high strength, the Young molar weight, (1,100GPa), breaking tenacity: (125GPa); 2, high heat conductance, (5,000W/mK); 3, high conductivity, carrier transport rate, (200,000cm
2/ V*s); 4, high specific surface area, (calculated value: 2,630m
2/ g).Wherein, the textural property of the nanoscale of the high conductivity matter of Graphene, large specific surface character and its unimolecular layer two dimension, make Graphene to be used as electrode materials in ultracapacitor and lithium ion battery.
Up to the present, known to the method for preparing Graphene have multiple, as: (1) micromechanics stripping method, this method can only produce the very limited graphene film of quantity, can be used as fundamental research; (2) ultrahigh vacuum(HHV) Graphene epitaxial growth method, the structural limitations of the expensive and sequin of this method its application; (3) chemical Vapor deposition process (CVD), this method can meet mass-producing and prepare the requirement of high-quality graphene, but cost is higher, complex process; (4) solvent stripping method, this method shortcoming are that productive rate is very low, limit its commercial applications; (5) oxidation-reduction method, this method is the simplest a kind of common method that can obtain in a large number Graphene, relatively method of reducing commonly used is chemical reduction (hydrazine hydrate, quadrol, sodium borohydride etc. are made reductive agent) and Rapid Thermal reduction, but after the whole bag of tricks reduction, all can there be the process of a reunion in Graphene, cause the specific surface area of Graphene less than normal, be generally less than 700m
2/ g.
Summary of the invention
For addressing the above problem, the present invention aims to provide a kind of method for preparing Graphene, and the method can effectively overcome a large amount of reunions of Graphene after reduction, and then can prepare the Graphene of high-specific surface area, and the method technique is simple, and the reaction times is short.
A kind of method for preparing Graphene provided by the invention comprises the following steps:
Getting graphite oxide is placed under protection of inert gas and carries out high temperature reduction; high temperature reduction is for reducing 10 ~ 60s at 800 ~ 1200 ℃ of temperature; subsequently the high temperature reduction product is taken out and is transferred to cooling 3 ~ 30s in liquid nitrogen, collect after cooling black powder and namely make Graphene.
After high temperature reduction, the high temperature reduction product be transferred to carry out in liquid nitrogen cooling.Usually, the temperature of liquid nitrogen is-196 ℃.At this moment, the huge temperature difference makes Graphene be more prone to fold, thereby effectively avoids the reunion of graphene film interlayer.
Preferably, the operating time of the high temperature reduction product being taken out and being transferred in liquid nitrogen is 1 ~ 5s.
Preferably, rare gas element is argon gas, nitrogen or helium, perhaps the mixed gas of any two kinds in argon gas, nitrogen and helium.
Preferably, the high temperature reduction reaction is carried out in high temperature process furnances.
Preferably, graphite oxide process drying treatment before carrying out high temperature reduction.More preferably, drying temperature is 60 ~ 100 ℃, and be 0.5 ~ 5h time of drying.
Preparation method of the present invention carries out cooled with liquid nitrogen fast after high temperature reduction, and unconventional room temperature that is cooled to after high temperature reduction, by contrast, in preparation method of the present invention, the huge temperature difference of high temperature reduction and cooled with liquid nitrogen makes Graphene be more prone to fold, thereby effectively avoids the reunion of graphene film interlayer.The Graphene specific surface area that the present invention makes is high, can reach 700 ~ 1500m
2/ g.
A kind of method for preparing Graphene provided by the invention can effectively overcome a large amount of reunions of Graphene after reduction, and then can prepare the Graphene of high-specific surface area, and the method technique is simple, and the reaction times is short.
Description of drawings
Fig. 1 is the Graphene that the embodiment of the present invention one makes.
Embodiment
The invention provides a kind of method for preparing Graphene, the method can effectively overcome a large amount of reunions of Graphene after reduction, and then can prepare the Graphene of high-specific surface area, and the method technique is simple, and the reaction times is short.
A kind of method for preparing Graphene provided by the invention comprises the following steps:
Getting graphite oxide is placed under protection of inert gas and carries out high temperature reduction; high temperature reduction is for reducing 10 ~ 60s at 800 ~ 1200 ℃ of temperature; subsequently the high temperature reduction product is taken out and is transferred to cooling 3 ~ 30s in liquid nitrogen, collect after cooling black powder and namely make Graphene.
After high temperature reduction, the high temperature reduction product be transferred to carry out in liquid nitrogen cooling.Usually, the temperature of liquid nitrogen is-196 ℃.At this moment, the huge temperature difference makes Graphene be more prone to fold, thereby effectively avoids the reunion of graphene film interlayer.
Preferably, the operating time of the high temperature reduction product being taken out and being transferred in liquid nitrogen is 1 ~ 5s.
Rare gas element is argon gas, nitrogen or helium, perhaps the mixed gas of any two kinds in argon gas, nitrogen and helium.
The high temperature reduction reaction is carried out in high temperature process furnances.
Graphite oxide is the process drying treatment before carrying out high temperature reduction.Drying temperature is 60 ~ 100 ℃, and be 0.5 ~ 5h time of drying.
Graphite oxide adopts following steps to make:
20g 50 order graphite (purity is 90% ~ 99.9%), 10g Potassium Persulphate and 10g Vanadium Pentoxide in FLAKES are added in the vitriol oil of 80 ℃, stir, cooling 6h, washing is to neutral, drying; Dried sample is added in 0 ℃, the vitriol oil of 230mL, then add 60g potassium permanganate, the temperature of mixture to remain on 20 ℃, after then keeping 2h in the oil bath of 35 ℃, slowly add the 920mL deionized water; After 15min, add again 2.8L deionized water (wherein contain 50mL concentration be 30% hydrogen peroxide), the mixture color becomes glassy yellow afterwards, suction filtration while hot, then with the hydrochloric acid that 5L concentration is 10%, wash, suction filtration, at 60 ℃ of vacuum-drying 48h, namely obtain graphite oxide.
Preparation method of the present invention carries out cooled with liquid nitrogen fast after high temperature reduction, and unconventional room temperature that is cooled to after high temperature reduction, by contrast, in preparation method of the present invention, the huge temperature difference of high temperature reduction and cooled with liquid nitrogen makes Graphene be more prone to fold, thereby effectively avoids the reunion of graphene film interlayer.The Graphene specific surface area that the present invention makes is high, can reach 700 ~ 1500m
2/ g.
A kind of method for preparing Graphene provided by the invention can effectively overcome a large amount of reunions of Graphene after reduction, and then can prepare the Graphene of high-specific surface area, and the method technique is simple, and the reaction times is short.
The following stated is the preferred embodiment of the present invention; should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also are considered as protection scope of the present invention.
The technical process that the present invention prepares Graphene is: graphite → graphite oxide → drying → high temperature reduction → cooled with liquid nitrogen → make Graphene.
Embodiment one
A kind of method for preparing Graphene comprises the following steps:
(1) prepare graphite oxide:
Get purity and be 99.5% the standby graphite oxide of graphite-made, its concrete steps are:
20g 50 order graphite, 10g Potassium Persulphate and 10g Vanadium Pentoxide in FLAKES are added in the vitriol oil of 80 ℃, stir, cooling 6h, washing is to neutral, drying; Dried sample is added in 0 ℃, the vitriol oil of 230mL, then add 60g potassium permanganate, the temperature of mixture to remain on 20 ℃, after then keeping 2h in the oil bath of 35 ℃, slowly add the 920mL deionized water; After 15min, add again 2.8L deionized water (wherein contain 50mL concentration be 30% hydrogen peroxide), the mixture color becomes glassy yellow afterwards, suction filtration while hot, then with the hydrochloric acid that 5L concentration is 10%, wash, suction filtration, at 60 ℃ of vacuum-drying 48h, namely obtain graphite oxide.
(2) drying: the graphite oxide that will obtain is at 60 ℃ of dry 5h.
(3) high temperature reduction: the 800 ℃ of reaction 60s of high temperature process furnances that dried graphite oxide put into argon shield;
(4) cooling: the high temperature reduction product is taken out and be transferred in 5s from high temperature process furnances carry out in liquid nitrogen cooling, reaction 3s, the powder of collecting black after reaction obtains the Graphene of high-specific surface area.
Fig. 1 is the SEM Electronic Speculum figure of the prepared Graphene of the embodiment of the present invention one, and as can be seen from Figure 1 graphite oxide is shelled into Graphene fully, and there is no and reunite.
Embodiment two
A kind of method for preparing Graphene comprises the following steps:
(1) prepare graphite oxide:
Get purity and be 99.5% the standby graphite oxide of graphite-made, its concrete steps are:
20g 50 order graphite, 10g Potassium Persulphate and 10g Vanadium Pentoxide in FLAKES are added in the vitriol oil of 80 ℃, stir, cooling 7h, washing is to neutral, drying; Dried sample is added in 0 ℃, the vitriol oil of 230mL, then add 60g potassium permanganate, the temperature of mixture to remain on 18 ℃, after then keeping 2h in the oil bath of 35 ℃, slowly add the 920mL deionized water; After 15min, add again 2.8L deionized water (wherein contain 50mL concentration be 30% hydrogen peroxide), the mixture color becomes glassy yellow afterwards, suction filtration while hot, then with the hydrochloric acid that 5L concentration is 10%, wash, suction filtration, at 60 ℃ of vacuum-drying 48h, namely obtain graphite oxide.
(2) drying: the graphite oxide that will obtain is at 80 ℃ of dry 3h.
(3) high temperature reduction: the 1000 ℃ of reaction 40s of high temperature process furnances that dried graphite oxide put into argon shield;
(4) cooling: the high temperature reduction product is taken out and be transferred in 2s from high temperature process furnances carry out in liquid nitrogen cooling, reaction 10s, the powder of collecting black after reaction obtains the Graphene of high-specific surface area.
Embodiment three
A kind of method for preparing Graphene comprises the following steps:
(1) prepare graphite oxide:
Get purity and be 99% the standby graphite oxide of graphite-made, its concrete steps are:
20g 50 order graphite, 10g Potassium Persulphate and 10g Vanadium Pentoxide in FLAKES are added in the vitriol oil of 80 ℃, stir, cooling 8h, washing is to neutral, drying; Dried sample is added in 0 ℃, the vitriol oil of 230mL, then add 60g potassium permanganate, the temperature of mixture to remain on 16 ℃, after then keeping 2h in the oil bath of 35 ℃, slowly add the 920mL deionized water; After 15min, add again 2.8L deionized water (wherein contain 50mL concentration be 30% hydrogen peroxide), the mixture color becomes glassy yellow afterwards, suction filtration while hot, then with the hydrochloric acid that 5L concentration is 10%, wash, suction filtration, at 60 ℃ of vacuum-drying 48h, namely obtain graphite oxide.
(2) drying: the graphite oxide that will obtain is at 80 ℃ of dry 2h.
(3) high temperature reduction: the 1100 ℃ of reaction 20s of high temperature process furnances that dried graphite oxide put into argon shield;
(4) cooling: the high temperature reduction product is taken out and be transferred in 0.5s from high temperature process furnances carry out in liquid nitrogen cooling, reaction 20s, the powder of collecting black after reaction obtains the Graphene of high-specific surface area.
Embodiment four
A kind of method for preparing Graphene comprises the following steps:
(1) prepare graphite oxide:
Get purity and be 99.9% the standby graphite oxide of graphite-made, its concrete steps are:
20g 50 order graphite, 10g Potassium Persulphate and 10g Vanadium Pentoxide in FLAKES are added in the vitriol oil of 80 ℃, stir, cooling 10h, washing is to neutral, drying; Dried sample is added in 0 ℃, the vitriol oil of 230mL, then add 60g potassium permanganate, the temperature of mixture to remain on 15 ℃, after then keeping 2h in the oil bath of 35 ℃, slowly add the 920mL deionized water; After 15min, add again 2.8L deionized water (wherein contain 50mL concentration be 30% hydrogen peroxide), the mixture color becomes glassy yellow afterwards, suction filtration while hot, then with the hydrochloric acid that 5L concentration is 10%, wash, suction filtration, at 60 ℃ of vacuum-drying 48h, namely obtain graphite oxide.
(2) drying: the graphite oxide that will obtain is at 100 ℃ of dry 0.5h.
(3) high temperature reduction: the 1200 ℃ of reaction 10s of high temperature process furnances that dried graphite oxide put into argon shield;
(4) cooling: the high temperature reduction product is taken out and be transferred in 3s from high temperature process furnances carry out in liquid nitrogen cooling, reaction 30s, the powder of collecting black after reaction obtains the Graphene of high-specific surface area.
The comparative example: step (1) ~ (3) are identical with front embodiment 3, the cooling naturally cooling that adopts of step (4), soon the product after step (3) high temperature reduction takes out and is placed on the room temperature naturally cooling from high temperature process furnances, and the powder of collecting black obtains Graphene.
The BET test result of the Graphene that table 1. embodiment 1 ~ 4 and comparative example make
| |
Embodiment 2 | Embodiment 3 | Embodiment 4 | The comparative example | |
| Specific surface area m 2/g | 729 | 972 | 1287 | 1511 | 700 |
BET (specific surface area method of testing) test result of the Graphene that table 1 makes for embodiment 1 ~ 4 and comparative example.As can be seen from Table 1, the specific surface area of the Graphene that makes of the embodiment of the present invention 1 ~ 4 is 729 ~ 1511m
2/ g, compare the specific surface area 700m of the Graphene that the comparative example makes
2/ g, have largely and improve.
Claims (6)
1. a method for preparing Graphene, is characterized in that, comprises the following steps:
Getting graphite oxide is placed under protection of inert gas and carries out high temperature reduction; described high temperature reduction is for reducing 10 ~ 60s at 800 ~ 1200 ℃ of temperature; subsequently the high temperature reduction product is taken out and is transferred to cooling 3 ~ 30s in liquid nitrogen, collect after cooling black powder and namely make Graphene.
2. the method for preparing Graphene as claimed in claim 1, is characterized in that, the described operating time that the high temperature reduction product is taken out and is transferred in liquid nitrogen is 1 ~ 5s.
3. the method for preparing Graphene as claimed in claim 1, is characterized in that, described rare gas element is argon gas, nitrogen or helium, perhaps the mixed gas of any two kinds in argon gas, nitrogen and helium.
4. the method for preparing Graphene as claimed in claim 1, is characterized in that, described high temperature reduction reaction is carried out in high temperature process furnances.
5. the method for preparing Graphene as claimed in claim 1, is characterized in that, described graphite oxide is the process drying treatment before carrying out high temperature reduction.
6. the method for preparing Graphene as claimed in claim 5, is characterized in that, the temperature of described drying treatment is 60 ~ 100 ℃, and the time is 0.5 ~ 5h.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104591169A (en) * | 2015-01-19 | 2015-05-06 | 清华大学深圳研究生院 | Self-dispersed graphite-like microcrystal material, dispersion liquid and preparation method of self-dispersed graphite-like microcrystal material |
| CN106496634A (en) * | 2016-10-14 | 2017-03-15 | 复旦大学 | A kind of preparation method of magnesium hydroxide Graphene composite heat-conducting insulating packing |
| CN106772779A (en) * | 2016-12-27 | 2017-05-31 | 东南大学 | A kind of enhanced plastic optical fiber and preparation method thereof |
| CN107021477A (en) * | 2017-05-26 | 2017-08-08 | 国家纳米科学中心 | A kind of method of macroscopic preparation of graphene and graphene oxide |
| CN110040722A (en) * | 2019-04-16 | 2019-07-23 | 中国科学院物理研究所 | A method of preparing graphene bubble |
| CN110155961A (en) * | 2018-06-25 | 2019-08-23 | 中国科学院物理研究所 | A method of preparing stratified material fold |
| CN110436448A (en) * | 2019-08-26 | 2019-11-12 | 上海利物盛纳米科技有限公司 | A kind of method of ultralow temperature preparation small size graphene dispersing solution |
| CN110577210A (en) * | 2018-06-07 | 2019-12-17 | 山东欧铂新材料有限公司 | preparation method of powder of graphene and graphene derivative |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104591169A (en) * | 2015-01-19 | 2015-05-06 | 清华大学深圳研究生院 | Self-dispersed graphite-like microcrystal material, dispersion liquid and preparation method of self-dispersed graphite-like microcrystal material |
| CN106496634A (en) * | 2016-10-14 | 2017-03-15 | 复旦大学 | A kind of preparation method of magnesium hydroxide Graphene composite heat-conducting insulating packing |
| CN106772779A (en) * | 2016-12-27 | 2017-05-31 | 东南大学 | A kind of enhanced plastic optical fiber and preparation method thereof |
| CN107021477A (en) * | 2017-05-26 | 2017-08-08 | 国家纳米科学中心 | A kind of method of macroscopic preparation of graphene and graphene oxide |
| CN110577210A (en) * | 2018-06-07 | 2019-12-17 | 山东欧铂新材料有限公司 | preparation method of powder of graphene and graphene derivative |
| CN110577210B (en) * | 2018-06-07 | 2023-04-25 | 山东欧铂新材料有限公司 | Preparation method of graphene and graphene derivative powder |
| CN110155961A (en) * | 2018-06-25 | 2019-08-23 | 中国科学院物理研究所 | A method of preparing stratified material fold |
| CN110155961B (en) * | 2018-06-25 | 2020-11-10 | 中国科学院物理研究所 | Method for preparing laminar material folds |
| CN110040722A (en) * | 2019-04-16 | 2019-07-23 | 中国科学院物理研究所 | A method of preparing graphene bubble |
| CN110040722B (en) * | 2019-04-16 | 2023-03-21 | 中国科学院物理研究所 | Method for preparing graphene bubbles |
| CN110436448A (en) * | 2019-08-26 | 2019-11-12 | 上海利物盛纳米科技有限公司 | A kind of method of ultralow temperature preparation small size graphene dispersing solution |
| CN110436448B (en) * | 2019-08-26 | 2021-07-02 | 上海利物盛纳米科技有限公司 | Method for preparing small-size graphene dispersion liquid at ultralow temperature |
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Application publication date: 20131113 |