CN101966988A - Method for preparing graphene powder - Google Patents
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- CN101966988A CN101966988A CN2010105478187A CN201010547818A CN101966988A CN 101966988 A CN101966988 A CN 101966988A CN 2010105478187 A CN2010105478187 A CN 2010105478187A CN 201010547818 A CN201010547818 A CN 201010547818A CN 101966988 A CN101966988 A CN 101966988A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a method for preparing graphene powder, which belongs to the field of graphene preparation and aims to solve the technical problems of low efficiency, low yield and environmental protection in the conventional graphene preparation methods. The method of the invention comprises the following steps of: 1, preparing graphite oxide; 2, stripping the graphite oxide; 3, performing purification, namely, performing centrifugation treatment and collecting upper-layer solution; and 4, controlling the reaction temperature to be above the supercritical temperature of a solvent in the step 2 to perform reaction for 1 to 24 hours under the conditions of the protection of an inert gas and the pressure of 20 to 100 MPa, naturally cooling or quenching with water a reaction kettle, and slowly exhausting the gas from the kettle to obtain the graphene powder. The graphene powder prepared by the method is goose feather-like black fluffy powder. The method of the invention has the advantages of the high efficiency of 100 percent, high yield and less environmental pollution.
Description
Technical field
The invention belongs to the Graphene preparation field.
Background technology
At present, the production method of Graphene mainly contains mechanically peel method, thermal expansion graphite method and chemical Vapor deposition process.The mechanically peel method, thermal expansion graphite method efficient is low, output is little, can only be limited to the laboratory small scale experiments.And chemical Vapor deposition process is also very immature at present.Recently scientist has been by having prepared the graphene oxide solution of controllable structure on a large scale with the method for potassium permanganate oxidation graphite in the vitriol oil, and reductive agent such as employing hydrazine reduces and obtains graphene aqueous solution.But this method has been used the bigger hydrazine of toxicity, and is difficult to obtain graphene powder.
In sum, existing preparation Graphene method exists that efficient is low, output is little, and to problem of environment pollution caused.
Summary of the invention
The present invention will solve existing preparation Graphene method and have that efficient is low, output is little, and to the technical problem of contaminate environment; And provide a kind of preparation method of Graphene powder.
The preparation method of Graphene powder is undertaken by following step among the present invention: one, the preparation of graphite oxide: 10g graphite is added in the mixture of strong oxidizing acid and nitrate, nitrate and graphite mass ratio are 0.2～1: 1, strong oxidizing acid and graphite mass ratio are 2～30: 1, be cooled to 0 ℃～5 ℃ then, stir 30～40min, continue to stir slowly to add simultaneously and contain the potassium strong oxidizer, describedly contain the potassium strong oxidizer and the graphite mass ratio is 0.4～6: 1, be warming up to 10～15 ℃ then, and continue to stir more than the 12h, subsequently liquid is imported temperature and be in 30～40 ℃ the water-bath, continue reaction 20～40min, slowly add 200ml water, be warming up to 90～100 ℃ and keep 35min, add hydrogen peroxide and 100ml water again, hydrogen peroxide and graphite mass ratio are 0.2～1: 1, continue to stir 2h, hydrochloric acid soln and water with 5% (quality) alternately clean 4 times, use flushing with clean water again, filter, the solid oven dry obtains oxidation graphite solid; Two, peel off graphite oxide: oxidation graphite solid is dissolved in the solvent, described solvent is water, ethanol, acetone, tetrahydrofuran (THF) or N, dinethylformamide is the 0.5～12h that vibrates under 300～1200W condition in hunting power then, promptly obtains graphene oxide solution; Three, purify: step 2 is obtained graphene oxide solution carry out centrifugal treating, collect upper solution, promptly obtain graphene oxide solution; Four, preparation Graphene: the graphene oxide solution that step 3 is obtained places in the supercritical reaction still; in protection of inert gas and pressure is under 20～100MPa condition; react 1～24h more than temperature of reaction being controlled at the supercritical temperature of step 2 solvent for use; reactor naturally cooling or water is crisp cold; lentamente gas in the still is emitted then, promptly obtain the Graphene powder.
The Graphene powder of the inventive method preparation is the fluffy powder of goose feather shape black, the products therefrom surface is connected to a lot of functional groups, as hydroxyl and carboxyl, oxygen level is about 21%, the prepared graphene powder in water, ethanol, tetrahydrofuran (THF), N, good dispersion in the dinethylformamide equal solvent.The inventive method increases the meltage of graphene oxide in water or ethanol, adopts the supercritical reaction still to increase useful volume, thereby improves output, and productive rate can reach 100% substantially.By to the weighing of graphite oxide and the weighing of product quality, productive rate reaches 100% substantially.The reductive agent gentleness that the present invention adopts, environmental pollution is little.
Description of drawings
Fig. 1 is embodiment nine preparation graphene powder photo figure; Fig. 2 is embodiment nine preparation graphene powder XRD figure; Fig. 3 is embodiment nine preparation graphene powders dispersive photos in water.
Embodiment
Embodiment one: the preparation method of Graphene powder is undertaken by following step in the present embodiment: one, the preparation of graphite oxide: 10g graphite is added in the mixture of strong oxidizing acid and nitrate, nitrate and graphite mass ratio are 0.2～1: 1, strong oxidizing acid and graphite mass ratio are 2～30: 1, be cooled to 0 ℃～5 ℃ then, stir 30～40min, continue to stir slowly to add simultaneously and contain potassium strong oxidizer (30min consuming time), describedly contain the potassium strong oxidizer and the graphite mass ratio is 0.4～6: 1, be warming up to 10～15 ℃ then, and continue to stir more than the 12h, subsequently liquid is imported temperature and be in 30～40 ℃ the water-bath, continue reaction 20～40min, slowly add 200ml water (30min consuming time), be warming up to 90～100 ℃ and keep 35min, add hydrogen peroxide and 100ml water again, hydrogen peroxide and graphite mass ratio are 0.2～1: 1, continue to stir 2h, hydrochloric acid soln and water with 5% (quality) alternately clean 4 times, use flushing with clean water again, filter, the filter cake oven dry is sieved after grinding again, obtains oxidation graphite solid; Two, peel off graphite oxide: oxidation graphite solid is dissolved in the solvent, described solvent is water, ethanol, acetone, tetrahydrofuran (THF) or N, dinethylformamide is the 0.5～12h that vibrates under 300～1200W condition in hunting power then, promptly obtains graphene oxide solution; Three, purify: step 2 is obtained graphene oxide solution carry out centrifugal treating, collect upper solution, promptly obtain graphene oxide solution; Four, the preparation of Graphene: the graphene oxide solution that step 3 is obtained places in the supercritical reaction still; in protection of inert gas and pressure is under 20～100MPa condition; react 1～24h more than temperature of reaction being controlled at the supercritical temperature of step 2 solvent for use; reactor naturally cooling or water is crisp cold; lentamente gas in the still is emitted then, promptly obtain the Graphene powder.
The Graphene powder of present embodiment preparation is the fluffy powder of goose feather shape black, and there are functional groups such as hydroxyl and carboxyl on the products therefrom surface; The prepared graphene powder is at water, ethanol, tetrahydrofuran (THF), N, good dispersion in the dinethylformamide equal solvent.
Embodiment two: what present embodiment and embodiment one were different is: the described graphite of step 1 is crystalline flake graphite.Other step is identical with embodiment one with parameter.
Embodiment three: what present embodiment was different with embodiment one or two is: the described strong oxidizing acid of step 1 is the vitriol oil or perchloric acid.Other step is identical with embodiment one or two with parameter.
Embodiment four: what present embodiment was different with one of embodiment one to three is: the described nitrate of step 1 is SODIUMNITRATE or saltpetre.Other step is identical with one of embodiment one to three with parameter.
Embodiment five: what present embodiment was different with one of embodiment one to four is: the described described potassium strong oxidizer that contains of step 1 is potassium permanganate or potassium perchlorate.Other step is identical with one of embodiment one to four with parameter.
Embodiment six: what present embodiment was different with one of embodiment one to five is: the described centrifugal rotation speed of step 3 is 3000～10000r/min.Other step is identical with one of embodiment one to five with parameter.
Embodiment seven: what present embodiment was different with one of embodiment one to six is: rare gas element described in the step 4 is nitrogen or argon gas.Other step is identical with one of embodiment one to six with parameter.
Embodiment eight: what present embodiment was different with one of embodiment one to seven is: pressure described in the step 4 is 40MPa.Other step is identical with one of embodiment one to seven with parameter.
Embodiment nine: the preparation method of Graphene powder is undertaken by following step in the present embodiment: one, the preparation of graphite oxide: it is 98% the vitriol oil and 5g NaNO that the 10g crystalline flake graphite is added the 100mL mass concentration
3Mixture in, be cooled to 5 ℃ then, stir 35min, continue to stir and slowly add 30g KMnO simultaneously
4(add KMnO
430min consuming time), be warming up to 10 ℃ then, and continue to stir 24 hours, subsequently liquid is imported temperature and be in 35 ℃ the water-bath, continue reaction 30min, slowly add 200mL deionized water (30min), be warming up to 100 ℃ and keep 35min, add 50mL hydrogen peroxide and 100mL deionized water again, continue to stir 2h, hydrochloric acid soln with 5% and water alternately clean 4 times, do not have in filtrate with flushing with clean water again
Till (use BaCl
2Solution detects), filter, with filter cake dry 48h under 100 ℃ of conditions, ground 200 mesh sieves, obtain oxidation graphite solid; Two, peel off graphite oxide: oxidation graphite solid is dissolved in the ethanol, is the 2h that vibrates under the 500W condition in hunting power then, promptly obtains graphene oxide solution (area of graphene oxide is many at 0.5-1 μ m); Three, purify: step 2 is obtained graphene oxide solution carry out centrifugal treating, collect upper solution, promptly obtain graphene oxide solution; Four, the preparation of Graphene: the graphene oxide solution that step 3 is obtained places in the supercritical reaction still; in protection of inert gas, temperature is that 400 ℃ and pressure are under the 20MPa condition; reaction 8h; water is crisp cold; lentamente gas in the still is emitted (deflation time is 8 hours) then, promptly obtain the Graphene powder.
The Graphene powder of present embodiment preparation is the fluffy powder (as shown in Figure 1) of goose feather shape black; A lot of functional groups is contained on the products therefrom surface, and as hydroxyl and carboxyl, oxygen level still reaches 21% (see figure 2); Prepared graphene powder good dispersion in water as shown in Figure 3.
Claims (7)
1. the preparation method of a Graphene powder, the preparation method who it is characterized in that the Graphene powder is undertaken by following step: one, the preparation of graphite oxide: 10g graphite is added in the mixture of strong oxidizing acid and nitrate, nitrate and graphite mass ratio are 0.2～1: 1, strong oxidizing acid and graphite mass ratio are 2～30: 1, be cooled to 0 ℃～5 ℃ then, stir 30～40min, continue to stir slowly to add simultaneously and contain the potassium strong oxidizer, describedly contain the potassium strong oxidizer and the graphite mass ratio is 0.4～6: 1, be warming up to 10～15 ℃ then, and continue to stir more than the 12h, subsequently liquid is imported temperature and be in 30～40 ℃ the water-bath, continue reaction 20～40min, slowly add 200mL water, be warming up to 90～100 ℃ and keep 35min, add hydrogen peroxide and 100mL water again, hydrogen peroxide and graphite mass ratio are 0.2～1: 1, continue to stir 2h, with mass concentration is that 5% hydrochloric acid soln and water alternately clean 4 times, use flushing with clean water again, filter, the filter cake oven dry, sieve after grinding again, obtain oxidation graphite solid; Two, peel off graphite oxide: oxidation graphite solid is dissolved in the solvent, described solvent is water, ethanol, acetone, tetrahydrofuran (THF) or N, dinethylformamide is the 0.5～12h that vibrates under 300～1200W condition in hunting power then, promptly obtains graphene oxide solution; Three, purify: step 2 is obtained graphene oxide solution carry out centrifugal treating, collect upper solution, promptly obtain graphene oxide solution; Four, the preparation of Graphene: the graphene oxide solution that step 3 is obtained places in the supercritical reaction still; in protection of inert gas and pressure is under 20～100MPa condition; react 1～24h more than temperature of reaction being controlled at the supercritical temperature of step 2 solvent for use; reactor naturally cooling or water is crisp cold; lentamente gas in the still is emitted then, promptly obtain the Graphene powder.
2. the preparation method of a kind of Graphene powder according to claim 1 is characterized in that the described graphite of step 1 is crystalline flake graphite.
3. the preparation method of a kind of Graphene powder according to claim 2 is characterized in that the described strong oxidizing acid of step 1 is the vitriol oil or perchloric acid.
4. the preparation method of a kind of Graphene powder according to claim 3 is characterized in that the described nitrate of step 1 is SODIUMNITRATE or saltpetre.
5. the preparation method of a kind of Graphene powder according to claim 4 is characterized in that the described described potassium strong oxidizer that contains of step 1 is potassium permanganate or potassium perchlorate.
6. the preparation method of a kind of Graphene powder according to claim 5 is characterized in that the described centrifugal rotation speed of step 3 is 3000～10000r/min.
7. according to the preparation method of the described a kind of Graphene powder of each claim among the claim 1-6, it is characterized in that rare gas element described in the step 4 is nitrogen or argon gas.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090155578A1 (en) * | 2007-12-17 | 2009-06-18 | Aruna Zhamu | Nano-scaled graphene platelets with a high length-to-width aspect ratio |
| CN101591014A (en) * | 2009-06-30 | 2009-12-02 | 湖北大学 | A kind of method of realizing large-scale preparation of monolayer oxidized graphene |
| US20100044646A1 (en) * | 2008-08-25 | 2010-02-25 | Aruna Zhamu | Supercritical fluid process for producing nano graphene platelets |
| US20100056819A1 (en) * | 2008-09-03 | 2010-03-04 | Jang Bor Z | Process for producing dispersible and conductive Nano Graphene Platelets from non-oxidized graphitic materials |
| US20100055458A1 (en) * | 2008-09-03 | 2010-03-04 | Jang Bor Z | Dispersible and conductive Nano Graphene Platelets |
-
2010
- 2010-11-17 CN CN2010105478187A patent/CN101966988B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090155578A1 (en) * | 2007-12-17 | 2009-06-18 | Aruna Zhamu | Nano-scaled graphene platelets with a high length-to-width aspect ratio |
| US20100044646A1 (en) * | 2008-08-25 | 2010-02-25 | Aruna Zhamu | Supercritical fluid process for producing nano graphene platelets |
| US20100056819A1 (en) * | 2008-09-03 | 2010-03-04 | Jang Bor Z | Process for producing dispersible and conductive Nano Graphene Platelets from non-oxidized graphitic materials |
| US20100055458A1 (en) * | 2008-09-03 | 2010-03-04 | Jang Bor Z | Dispersible and conductive Nano Graphene Platelets |
| CN101591014A (en) * | 2009-06-30 | 2009-12-02 | 湖北大学 | A kind of method of realizing large-scale preparation of monolayer oxidized graphene |
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