CN103771395A - Graphene material and preparation method thereof - Google Patents
Graphene material and preparation method thereof Download PDFInfo
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- CN103771395A CN103771395A CN201210406041.1A CN201210406041A CN103771395A CN 103771395 A CN103771395 A CN 103771395A CN 201210406041 A CN201210406041 A CN 201210406041A CN 103771395 A CN103771395 A CN 103771395A
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Abstract
The invention provides a preparation method for a graphene material. The preparation method comprises the following steps: adding graphite oxide into water and carrying out ultrasonic treatment for 0.5 to 3 h so as to obtain a graphene oxide suspension; adding the graphene oxide suspension into a phosphoric acid solution and carrying out stirring for 1 to 3 h so as to obtain a graphene oxide-phosphoric acid mixed solution; drying the graphene oxide-phosphoric acid mixed solution in a baking oven until the mixed solution becomes a loose block, putting the block into a reactor, carrying out heating to a temperature of 500 to 900 DEG C and carrying out a reaction for 0.5 to 2 h with the temperature maintained; and naturally cooling the reactor to 20 to 50 DEG C, taking out a reaction product, washing the reaction product with deionized water and then drying the reaction product so as to obtain the graphene material. The invention further provides the graphene material prepared by using the method. According to the invention, nontoxic and harmless phosphoric acid is used to treat graphite oxide, so the specific surface area of graphene is increased; the preparation method is simple, has low cost and exerts no negative effects on equipment and an external environment.
Description
Technical field
The present invention relates to the synthetic field of material, relate in particular to a kind of grapheme material and preparation method thereof.
Background technology
Graphene is between a kind of carbon atom, to be the two-dimensional sheet body that hexagonal annular is arranged, and the people such as the strong K sea nurse of the peace moral by Univ Manchester UK in 2004 (Andre K.Geim) find first.Grapheme material has good conduction, heat conductivility and low thermal expansivity, and its theoretical specific surface area is up to 2630m
2/ g, thus be widely used in that effect transistor, liquid crystal are looked, battery, the each field of sensor.
The method of preparing at present Graphene is mainly oxidation reduction process, be specially and first graphite made under the effect of strong acid and strong oxidizer to the graphite oxide of easily peeling off, then the graphene oxide that forms individual layer by ultrasonic method, is finally reduced to grapheme material by method of reducing such as strong reductant reduction, high-temperature heating treatment, microwave exposure processing, electrochemical reductions by mono-layer graphite oxide alkene again.This method cost is low, yield is high, easy to control, is applicable to suitability for industrialized production on a large scale.But because Graphene is easily reunited in the process of reduction, the Graphene that existing chemical reduction method makes often specific surface area is less than normal, is generally less than 700m
2/ g.How to improve its table specific area, become one of focus of grapheme material research field.
Patent CN102070140A has reported a kind of method of utilizing highly basic processing to obtain preparing high-specific surface area graphene material, the method is utilized the reaction at high temperature of highly basic and carbon, the graphene powder that thermal treatment or microwave exposure are obtained carries out further chemical treatment, thereby fast, the large batch of micropore that goes out nanometer scale in Graphene surface corrosion, greatly improve its specific surface area.But because highly basic has severe corrosive, adopt the method to carry out the transformation of Graphene, can produce comparatively serious detrimental effect to equipment, and easily environment be produced to larger negative impact.
Summary of the invention
The object of the invention is to overcome prior art adopts highly basic to process the defect that the easy etching apparatus generation of raising Graphene specific surface area is polluted, a kind of preparation method and grapheme material obtained by this method of grapheme material are provided, preparation method's technique is simple, cost is low, equipment and external environment is not had a negative impact.
The present invention solves the problems of the technologies described above adopted scheme:
First aspect, the invention provides a kind of preparation method of grapheme material, comprises the following steps: first, graphite oxide is added to the water, ultrasonic 0.5～3 hour, obtaining concentration was 0.1 ~ 5g/L graphene oxide suspension; Then, the ratio that is 1:0.5～5 in the mass ratio of graphene oxide and phosphoric acid solution by described graphene oxide suspension joins in phosphoric acid solution, stirs and within 1～3 hour, obtains graphene oxide-phosphoric acid mixed solution; Then, described graphene oxide-phosphoric acid mixed solution is put into after baking oven is dried to loose bulk and put into reactor, with the heat-up rate of 5 ~ 20 ℃/min, the temperature in reactor is risen to 500～900 ℃, insulation reaction 0.5～2 hour; Finally, take out reactant after reactor is naturally cooled to 20～50 ℃, with dry after deionized water wash, obtain grapheme material.
Preferably, described graphite oxide adopts following steps to make:
In mass ratio the ratio of 2:1:1 get the vitriol oil that Graphite Powder 99, Potassium Persulphate and Vanadium Pentoxide in FLAKES add 80 ℃ and stir after cooling 6～10 hours, filtration drying, then filter residue is joined in the vitriol oil of 0 ℃, add again potassium permanganate, after mixing, keeping the temperature of mixed solution is 0～10 ℃, then oil bath 2～3 hours at 35～40 ℃; Add deionized water, after 15～30 minutes, add hydrogen peroxide again in mixed solution, suction filtration while hot, washs solids with dilute hydrochloric acid and deionized water successively, and suction filtration drying solid thing, obtain graphite oxide.The solid-to-liquid ratio of the vitriol oil of described Graphite Powder 99 and described 0 ℃ is 1g:10～15mL; The mass ratio of described Graphite Powder 99 and described potassium permanganate is 1:3～5; The solid-to-liquid ratio of potassium permanganate and hydrogen peroxide is 1g:40～50mL.
Preferably, the purity of described Graphite Powder 99 is 90% ~ 99.9%, and particle diameter is 50～500 orders.
The graphite oxide that adopts above-mentioned preparation method to prepare, its degree of oxidation is higher, more favourable its follow-up peeling off, graphite oxide is peeled off into the combination that is more conducive to itself and phosphoric acid after the graphene oxide of lamella, can further improve the specific surface area of final product Graphene.
Preferably, the concentration of described phosphoric acid solution is 50 ~ 80%.
Preferably, described reactor is cremator, retort furnace or graphite furnace.
Preparation method of the present invention adopts phosphoric acid to process graphite oxide, in the time of 200～300 ℃, phosphoric acid is cross-linked by the oxygen-containing functional group in mode and the graphite oxide of polycondensation and cyclisation, forms stable polycondensation carbon structure, can effectively prevent the reunion of sheet layer architecture.After temperature rise to 500 ℃, having phosphoric acid carbon structure gasification anti-oxidant, heat-resisting ability overflows, overflowing of gas struts graphene sheet layer structure, prevent that Graphene from forming abundant pore structure when reunion, and then increasing specific surface area, preparation method's technique is simple, and cost is low, equipment is not produced to infringement, also can not cause environmental pollution.
Second aspect, the invention provides a kind of grapheme material, and described grapheme material makes by above-mentioned preparation method.
Grapheme material prepared by the present invention has passed through phosphoric acid processing, and graphene film layer architecture is difficult for reuniting, and contains abundant pore structure, and table specific area is high.
A kind of grapheme material provided by the invention and preparation method thereof, has following beneficial effect:
(1) with nontoxic phosphoric acid, graphite oxide is processed, improved the specific surface area of the Graphene of preparation, preparation method's technique is simple, and cost is low, equipment and external environment is not had a negative impact.
(2) grapheme material has passed through phosphoric acid processing, and graphene film layer architecture is difficult for reuniting, and contains abundant pore structure, and specific surface area is high.
Embodiment
Below in conjunction with specific embodiment, the technical scheme in embodiment of the present invention is clearly and completely described.
Embodiment mono-
A preparation method for grapheme material, comprises the following steps:
Getting 20g purity and be 99.5% particle diameter and be 50 object Graphite Powder 99s, 10g Potassium Persulphate and 10g Vanadium Pentoxide in FLAKES, to add 1L temperature be in 80 ℃ of concentration vitriol oil that is 90%, stir after 15 minutes cooling 6 hours, leaching filter residue and with deionized water wash to the pH of elutant be 7, put at 50 ℃, baking oven dry 2 hours; Then in the vitriol oil that filter residue to be joined to 230mL temperature and be 0 ℃ of concentration be 98%, then add 60g potassium permanganate, after mixing, keeping the temperature of mixed solution is 10 ℃, then oil bath 2 hours in the oil cauldron of 35 ℃; Slowly add 950mL deionized water, after 15 minutes, be that 15% hydrogen peroxide is removed potassium permanganate to adding 2.8L concentration in mixed solution again, suction filtration while hot, the hydrochloric acid that is 10% by 5L concentration successively and 1L deionized water wash solids, solids is poured in cloth formula funnel and carried out suction filtration again, after suction filtration, solids is put into vacuum drying oven, 60 ℃ are dried 48 hours, obtain graphite oxide.
Get the above-mentioned graphite oxide of 10g and join in 10mL deionized water, supersound process 0.5 hour, obtains graphene oxide suspension; Then, it is in 50% phosphoric acid solution that described graphene oxide suspension is joined to 3.8mL concentration, stirs and within 1 hour, obtains graphene oxide-phosphoric acid mixed solution; Then, described graphene oxide-phosphoric acid mixed solution is put into after baking oven is dried to loose bulk and put into cremator, with the heat-up rate of 15 ℃/min, the temperature in reactor is warming up to 500 ℃, insulation reaction 2 hours; Finally, taking out reactant after cremator is naturally cooled to 50 ℃, is to put into baking oven after 7 with deionized water rinsing to the pH of elutant, 60 ℃ dry 2 hours, obtain grapheme material.
Embodiment bis-
A preparation method for grapheme material, comprises the following steps:
Getting 10g purity and be 90% particle diameter and be 200 object Graphite Powder 99s, 5g Potassium Persulphate and 5g Vanadium Pentoxide in FLAKES, to add 200mL temperature be in 80 ℃ of concentration vitriol oil that is 98%, stir after 15 minutes cooling 7 hours, leaching filter residue and with deionized water wash to the pH of elutant be 6, put at 80 ℃, baking oven dry 1 hour; Then in the vitriol oil that filter residue to be joined to 125mL temperature and be 0 ℃ of concentration be 98%, then add 50g potassium permanganate, after mixing, keeping the temperature of mixed solution is 0 ℃, then oil bath 2 hours in the oil cauldron of 40 ℃; Slowly add 475mL deionized water, after 30 minutes, be that 15% hydrogen peroxide is removed potassium permanganate to adding 1.2L concentration in mixed solution again, suction filtration while hot, the hydrochloric acid that is 10% by 2L concentration successively and 1L deionized water wash solids, solids is poured in cloth formula funnel and carried out suction filtration again, after suction filtration, solids is put into vacuum drying oven, 60 ℃ are dried 48 hours, obtain graphite oxide.
Get the above-mentioned graphite oxide of 1g and join in 1mL deionized water, supersound process 3 hours, obtains graphene oxide suspension; Then, it is in 80% phosphoric acid solution that described graphene oxide suspension is joined to 3mL concentration, stirs and within 3 hours, obtains graphene oxide-phosphoric acid mixed solution; Then, described graphene oxide-phosphoric acid mixed solution is put into after baking oven is dried to loose bulk and put into retort furnace, with the heat-up rate of 20 ℃/min, the temperature in reactor is warming up to 900 ℃, insulation reaction 0.5 hour; Finally, taking out reactant after retort furnace is naturally cooled to 20 ℃, is to put into baking oven after 6 with deionized water rinsing to the pH of elutant, 80 ℃ dry 1 hour, obtain grapheme material.
Embodiment tri-
A preparation method for grapheme material, comprises the following steps:
Getting 20g purity and be 99.9% particle diameter and be 500 object Graphite Powder 99s, 10g Potassium Persulphate and 10g Vanadium Pentoxide in FLAKES, to add 1L temperature be in 80 ℃ of concentration vitriol oil that is 98%, stir after 30 minutes cooling 10 hours, leaching filter residue and with deionized water wash to the pH of elutant be 7, put at 60 ℃, baking oven dry 2 hours; Then in the vitriol oil that filter residue to be joined to 230mL temperature and be 0 ℃ of concentration be 90%, then add 60g potassium permanganate, after mixing, keeping the temperature of mixed solution is 10 ℃, then oil bath 3 hours in the oil cauldron of 35 ℃; Slowly add 950mL deionized water, after 15 minutes, be that 15% hydrogen peroxide is removed potassium permanganate to adding 2.8L concentration in mixed solution again, suction filtration while hot, the hydrochloric acid that is 10% by 3L concentration successively and 1L deionized water wash solids, solids is poured in cloth formula funnel and carried out suction filtration again, after suction filtration, solids is put into vacuum drying oven, 60 ℃ are dried 48 hours, obtain graphite oxide.
Get the above-mentioned graphite oxide of 6g and join in 10mL deionized water, supersound process 1 hour, obtains graphene oxide suspension; Then, it is in 60% phosphoric acid solution that described graphene oxide suspension is joined to 4.2mL concentration, stirs and within 1 hour, obtains graphene oxide-phosphoric acid mixed solution; Then, described graphene oxide-phosphoric acid mixed solution is put into after baking oven is dried to loose bulk and put into graphite furnace, with the heat-up rate of 5 ℃/min, the temperature in reactor is warming up to 600 ℃, insulation reaction 2 hours; Finally, taking out reactant after graphite furnace is naturally cooled to 40 ℃, is to put into vacuum drying oven after 7 with deionized water rinsing to the pH of elutant, 50 ℃ dry 3 hours, obtain grapheme material.
Embodiment tetra-
A preparation method for grapheme material, comprises the following steps:
Getting 100g purity and be 99.5% particle diameter and be 50 object Graphite Powder 99s, 50g Potassium Persulphate and 50g Vanadium Pentoxide in FLAKES, to add 5L temperature be in 80 ℃ of concentration vitriol oil that is 98%, stir after 15 minutes cooling 10 hours, leaching filter residue and with deionized water wash to the pH of elutant be 7, put at 60 ℃, baking oven dry 2 hours; Then in the vitriol oil that filter residue to be joined to 1L temperature and be 0 ℃ of concentration be 98%, then add 400g potassium permanganate, after mixing, keeping the temperature of mixed solution is 5 ℃, then oil bath 2 hours in the oil cauldron of 40 ℃; Slowly add 5L deionized water, after 30 minutes, be that 15% hydrogen peroxide is removed potassium permanganate to adding 10L concentration in mixed solution again, suction filtration while hot, the hydrochloric acid that is 10% by 10L concentration successively and 5L deionized water wash solids, solids is poured in cloth formula funnel and carried out suction filtration again, after suction filtration, solids is put into vacuum drying oven, 60 ℃ are dried 48 hours, obtain graphite oxide.
Get the above-mentioned graphite oxide of 50g and join in 100mL deionized water, supersound process 2 hours, obtains graphene oxide suspension; Then, it is in 70% phosphoric acid solution that described graphene oxide suspension is joined to 65.5mL concentration, stirs and within 2 hours, obtains graphene oxide-phosphoric acid mixed solution; Then, described graphene oxide-phosphoric acid mixed solution is put into after baking oven is dried to loose bulk and put into cremator, with the heat-up rate of 10 ℃/min, the temperature in reactor is warming up to 800 ℃, insulation reaction 1 hour; Finally, taking out reactant after graphite furnace is naturally cooled to 50 ℃, is to put into baking oven after 7 with deionized water rinsing to the pH of elutant, 70 ℃ dry 2 hours, obtain grapheme material.
Comparative example
A preparation method for grapheme material, comprises the following steps:
Getting 20g purity and be 99.5% particle diameter and be 50 object Graphite Powder 99s, 10g Potassium Persulphate and 10g Vanadium Pentoxide in FLAKES, to add 1L temperature be in 80 ℃ of concentration vitriol oil that is 90%, stir after 15 minutes cooling 6 hours, leaching filter residue and with deionized water wash to the pH of elutant be 7, put at 50 ℃, baking oven dry 2 hours; Then in the vitriol oil that filter residue to be joined to 230mL temperature and be 0 ℃ of concentration be 98%, then add 60g potassium permanganate, after mixing, keeping the temperature of mixed solution is 10 ℃, then oil bath 2 hours in the oil cauldron of 35 ℃; Slowly add 950mL deionized water, after 15 minutes, be that 15% hydrogen peroxide is removed potassium permanganate to adding 2.8L concentration in mixed solution again, suction filtration while hot, the hydrochloric acid that is 10% by 5L concentration successively and 1L deionized water wash solids,, then solids is poured in cloth formula funnel and carried out suction filtration, after suction filtration, solids is put into vacuum drying oven, 60 ℃ are dried 48 hours, obtain graphite oxide.
Above-mentioned graphite oxide is put into retort furnace, in retort furnace, pass into argon gas and with the heat-up rate of 15 ℃/min, the temperature in retort furnace is risen to 1050 ℃, high temperature reduction 30 seconds, obtains grapheme material.
Effect embodiment
The specific surface area of the grapheme material described in employing BET specific surface area method of testing test implementation example one to four and comparative example, test result is as table 1.
The specific surface area test result of grapheme material prepared by the each embodiment of table 1
The specific surface area of the grapheme material that as can be seen from Table 1, prepared by the embodiment of the present invention is 976 ~ 1286m
2/ g, is significantly higher than the prepared grapheme material of comparative example.
The above is the preferred embodiment of the present invention; it 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 are also considered as protection scope of the present invention.
Claims (7)
1. a preparation method for grapheme material, is characterized in that, comprises the following steps: first, graphite oxide is added to the water, ultrasonic 0.5～3 hour, obtaining concentration was 0.1 ~ 5g/L graphene oxide suspension; Then, the ratio that is 1:0.5～5 in the mass ratio of graphene oxide and phosphoric acid solution by described graphene oxide suspension joins in phosphoric acid solution, stirs and within 1～3 hour, obtains graphene oxide-phosphoric acid mixed solution; Then, described graphene oxide-phosphoric acid mixed solution is put into after baking oven is dried to loose bulk and put into reactor, with the heat-up rate of 5 ~ 20 ℃/min, the temperature in reactor is risen to 500～900 ℃, insulation reaction 0.5～2 hour; Finally, take out reactant after reactor is naturally cooled to 20～50 ℃, with dry after deionized water wash, obtain grapheme material.
2. the preparation method of a kind of grapheme material according to claim 1, is characterized in that, described graphite oxide adopts following steps to make:
In mass ratio the ratio of 2:1:1 get the vitriol oil that Graphite Powder 99, Potassium Persulphate and Vanadium Pentoxide in FLAKES add 80 ℃ and stir after cooling 6～10 hours, filtration drying, then filter residue is joined in the vitriol oil of 0 ℃, add again potassium permanganate, after mixing, keeping the temperature of mixed solution is 0～10 ℃, then oil bath 2～3 hours at 35～40 ℃; Add deionized water, after 15～30 minutes, add hydrogen peroxide again in mixed solution, suction filtration while hot, washs solids with dilute hydrochloric acid and deionized water successively, and suction filtration drying solid thing, obtain graphite oxide.The solid-to-liquid ratio of the vitriol oil of described Graphite Powder 99 and described 0 ℃ is 1g:10～15mL; The mass ratio of described Graphite Powder 99 and described potassium permanganate is 1:3～5; The solid-to-liquid ratio of potassium permanganate and hydrogen peroxide is 1g:40～50mL.
3. the preparation method of a kind of grapheme material according to claim 2, is characterized in that, the purity of described Graphite Powder 99 is 90% ~ 99.9%, and particle diameter is 50～500 orders.
4. the preparation method of a kind of grapheme material according to claim 1, is characterized in that, the concentration of described phosphoric acid solution is 50 ~ 80%.
5. the preparation method of a kind of grapheme material according to claim 1, is characterized in that, described reactor is cremator, retort furnace or graphite furnace.
6. the preparation method of a kind of grapheme material according to claim 1, is characterized in that, the intensification of described reactor, and heat-up rate is 15 ℃/min.
7. a grapheme material, is characterized in that, described grapheme material is made by preparation method described in any one in claim 1～6.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105922413A (en) * | 2016-04-21 | 2016-09-07 | 东北林业大学 | Preparation method of magnetic wood material for absorbing electromagnetic wave |
| CN109110752A (en) * | 2018-10-31 | 2019-01-01 | 新疆烯金石墨烯科技有限公司 | Multistage low-temp reaction method prepares graphene oxide, graphene and preparation method thereof |
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| CN102701187A (en) * | 2011-07-13 | 2012-10-03 | 华东理工大学 | Preparation method of graphene and graphene prepared by same |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102701187A (en) * | 2011-07-13 | 2012-10-03 | 华东理工大学 | Preparation method of graphene and graphene prepared by same |
Non-Patent Citations (2)
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| M.MOLINA-SABIO ET AL.: "Role of chemical activation in the development of carbon porosity", 《COLLOIDS AND SURFACES A: PHYSICOCHEM. ENG. ASPECTS》 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105922413A (en) * | 2016-04-21 | 2016-09-07 | 东北林业大学 | Preparation method of magnetic wood material for absorbing electromagnetic wave |
| CN105922413B (en) * | 2016-04-21 | 2017-04-26 | 东北林业大学 | Preparation method of magnetic wood material for absorbing electromagnetic wave |
| CN109110752A (en) * | 2018-10-31 | 2019-01-01 | 新疆烯金石墨烯科技有限公司 | Multistage low-temp reaction method prepares graphene oxide, graphene and preparation method thereof |
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Application publication date: 20140507 |