CN105645384A - Preparation method of graphene - Google Patents
Preparation method of graphene Download PDFInfo
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- CN105645384A CN105645384A CN201410720840.5A CN201410720840A CN105645384A CN 105645384 A CN105645384 A CN 105645384A CN 201410720840 A CN201410720840 A CN 201410720840A CN 105645384 A CN105645384 A CN 105645384A
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Abstract
Belonging to the technical field of carbon materials, the invention discloses a preparation method of multilayer graphene. The method consists of: taking natural flake graphite as the raw material, carrying out two oxidation, cleaning, solid-liquid separation and drying to obtain multilayer graphene. The multilayer grapheme prepared by the method provided by the invention has a specific surface area of 190-350m<2>/g, an average pore size of about 3.8nm, and a pore volume of 0.6-1.5cm<2>/g. The method provided by the invention has no need for high-temperature treatment, has low energy consumption in production, needs no catalyst or strong reducing agent, also can recover and reuse the solvent involved in the production process, can lower the cost, and is also beneficial to environmental protection. The method provided by the invention has the characteristics of simple process, convenient operation, and little production equipment, further lowers the cost, is convenient for popularization and application, and is suitable for mass production. The multilayer graphene prepared by the method provided by the invention can be used as an electrode material of batteries and supercapacitors, and can also be used a conductive agent for lithium ion batteries, alkaline batteries, and nickel-hydrogen batteries.
Description
Technical field
The invention belongs to carbon material technical field, specifically relate to the preparation method of a kind of Graphene.
Background technology
Graphene is with sp by monolayer carbon atom2The nano-carbon material with six square lattice polynuclear planes that hybrid form bonding is formed, belongs to a kind of novel two dimensional crystal material. Graphene has good electroconductibility, thermal conductivity, mechanical property, light transmission and electronics property, is with a wide range of applications in stored energy, opto-electronic device and field of compound material. Therefore, Graphene has become the research focus in multiple subject fields such as materialogy, physics and chemistry at present. In industrialization, due to the development of various technology of preparing, the exploitation of graphene product also achieves in recent years and is in progress significantly.
At present, the preparation method of Graphene has: mechanically peel method, chemical Vapor deposition process and oxidation-reduction method. The output of mechanically peel method and process for preparing graphenes by chemical vapour deposition is very low, and the complex process of chemical Vapor deposition process, it is necessary to removing catalyzer specially, energy consumption is big, and production cost is too high, is not suitable with the requirement of scale operation. Oxidation-reduction method obtains graphite oxide after mainly utilizing hydrogen-oxygen agent to be oxidized by natural flake graphite, and then ultrasonic stripping obtains graphene oxide, then obtains grapheme material after reduction. But the graphene oxide obtained is a kind of two-dimensional slice shape structure, good dispersity in water, adopts the common methods such as filter, centrifugation of taking out to be difficult to separate graphene oxide from its aqueous solution; And often adopt strong reductant (hydrazine hydrate, hypertoxic type) or high temperature (high energy consumption) that graphene oxide is carried out reduction treatment, it is very difficult to meet the standard of Green synthesis. Particularly to extensive industry preparation and process, these method cost height, efficiency is low, should not apply. Therefore, explore the method for the reduction-oxidation graphite of a kind of simple and practical, economical and efficient, environmental protection, to the extensive preparation solving Graphene, it is achieved the widespread use of Graphene has very important value.
Summary of the invention
It is an object of the invention to overcome the deficiency of existing graphene preparation method, it is provided that a kind of novel method preparing multi-layer graphene by graphite oxide. The method has that technique is simple, easy to operate, production cost is low, be suitable for the advantages such as scale operation.
The implementation of the object of the invention is, a kind of method preparing multi-layer graphene on a large scale, and concrete steps are as follows:
1. graphite oxide: the preparation of graphite oxide adopts twice oxidation to complete.
1.1 once oxidations: be raw material taking natural flake graphite, utilize oxygenant preoxidation, are oxidized after 4��8 hours, deionized water wash is utilized to take out filter to neutral, Air drying, the oxygenant that once oxidation adopts is the composition of the vitriol oil, ammonium persulphate and Vanadium Pentoxide in FLAKES;
1.2 secondary oxidations: get the raw material after once oxidation, it is re-dispersed in the vitriol oil, utilize potassium permanganate to be oxidized by the raw material after once oxidation as co-oxidation agent simultaneously, react and within 2 hours, add deionized water dilution, in dilution, system temperature controls below 50 degrees Celsius, and the hydrogen peroxide adding 30% subsequently completes secondary oxidation.
2. by the product after oxidation, first dilute hydrochloric acid is utilized to clean, remove the remaining metal ion in product and sulfate ion etc., then low boiling-point and polarity organic solvent is utilized to clean to neutral, and it is re-dispersed in low boiling-point and polarity organic solvent, obtained suspension liquid, low boiling-point and polarity organic solvent comprises: acetone, methyl alcohol, ethanol etc.
3. solid-liquid separation: the suspension liquid obtained by step 2, adopts the method for centrifugation, mixing solutions is carried out solid-liquid separation, collects solvent and graphite oxide respectively.
4. prepare multi-layer graphene: cleaning the organic solvent that utilizes of wet state to neutral graphite oxide, drying 60��300 minutes, can obtain multi-layer graphene under temperature is 80��150 degrees Celsius.
After the present invention adopts technique scheme, mainly contain following effect:
(1) the present invention prepares the multi-layer graphene specific surface area at 190��350m2Between/g, mean pore size at about 3.8nm, Kong Rong at 0.6��1.5cm2Between/g;
(2) the inventive method is without the need to pyroprocessing, and production energy consumption is low;
(3) the inventive method is without the need to catalyzer, it is not necessary to strong reductant, to the solvent in production process can also recycling, can reduce costs, be conducive to again environmental protection;
(4) technique of the present invention is simple, and easy to operate, production unit is few, thus reduces costs further, easy to utilize, is suitable for scale production.
Adopting the inventive method to prepare the multi-layer graphene can as the electrode materials of battery, ultracapacitor, it is possible to as the conductive agent of lithium ion battery, alkaline cell, Ni-H cell.
Accompanying drawing explanation
Fig. 1 utilizes the stereoscan photograph of the multi-layer graphene that acetone prepared as solvent
Fig. 2 utilizes the transmission electron microscope photo of the multi-layer graphene that acetone prepared as solvent
Fig. 3 utilizes the multi-layer graphene adsorption desorption curve and relevant characteristic that acetone prepared as solvent
Fig. 4 utilizes the multi-layer graphene adsorption desorption curve and relevant characteristic that methyl alcohol prepared as solvent
Fig. 5 utilizes the multi-layer graphene adsorption desorption curve and relevant characteristic that ethanol (110 degrees Celsius) prepared as solvent
Fig. 6 utilizes the multi-layer graphene adsorption desorption curve and relevant characteristic that ethanol (120 degrees Celsius) prepared as solvent
Embodiment
Below in conjunction with embodiment and accompanying drawing, the invention will be further described, but it is not the restriction to invention.
Embodiment 1
Take 3 grams of natural flake graphites, it is scattered in 120 milliliters of vitriol oils, add 0.5 gram of ammonium persulphate and 0.5 gram of Vanadium Pentoxide in FLAKES, react 4 hours under 80 degrees celsius, take out filter to neutral, Air drying with deionized water wash subsequently; By dried product, being again dispersed in 100 milliliters of vitriol oils, and add 15 grams of potassium permanganate, reaction system is placed in ice bath, reacts after 2 hours, adds 210 ml deionized water dilutions, adds the hydrogen peroxide of 30 milliliter 30% subsequently, obtain graphite oxide.
Then utilize the dilute hydrochloric acid of 0.01 mole often liter to clean graphite oxide and remove excess metal ion and sulfate radical, clean to neutral with acetone subsequently, after centrifugal, obtain neutral alumina graphite.
The graphite oxide of wet state is put into baking oven, 80 degrees Celsius of dryings, it is incubated 6 hours, multi-layer graphene can be obtained.
Embodiment 2
Utilizing methyl alcohol to replace the acetone in example 1, dry under 90 degrees celsius, insulation, can obtain multi-layer graphene material equally.
Embodiment 3
Utilizing ethanol to replace the acetone in example 1, dry under 110 degrees celsius, insulation, can obtain multi-layer graphene material equally.
Embodiment 4
Utilizing ethanol to replace the acetone in example 1, dry under 120 degrees celsius, insulation, can obtain multi-layer graphene material equally.
Claims (5)
1. the preparation method of a multi-layer graphene, it is characterised in that concrete method steps is as follows:
(1) graphite oxide: the preparation of graphite oxide adopts twice oxidation to complete.
Once oxidation: be raw material taking natural flake graphite, utilizes oxygenant preoxidation, is oxidized after 4��8 hours, utilizes deionized water wash to take out filter to neutral, Air drying, and the oxygenant that once oxidation adopts is the composition of the vitriol oil, ammonium persulphate and Vanadium Pentoxide in FLAKES;
Secondary oxidation: get the raw material after once oxidation, it is re-dispersed in the vitriol oil, utilize potassium permanganate to be oxidized by the raw material after once oxidation as co-oxidation agent simultaneously, react and within 2 hours, add deionized water dilution, in dilution, system temperature controls below 50 degrees Celsius, and the hydrogen peroxide adding 30% subsequently completes secondary oxidation.
(2) clean: by the product after oxidation, first utilize dilute hydrochloric acid to clean, remove the remaining metal ion in product and sulfate ion etc., then utilize low boiling-point and polarity organic solvent to clean to neutral, and it is re-dispersed in low boiling-point and polarity organic solvent, obtained suspension liquid. Low boiling-point and polarity organic solvent comprises: acetone, methyl alcohol, ethanol etc.
(3) solid-liquid separation: the suspension liquid obtained by step (2), adopts the method for centrifugation, mixing solutions is carried out solid-liquid separation, collects solvent and graphite oxide respectively.
(4) multi-layer graphene is prepared: cleaning the organic solvent that utilizes of wet state to neutral graphite oxide, drying 60��300 minutes, can obtain multi-layer graphene under temperature is 80��150 degrees Celsius.
2. according to the preparation method of a kind of multi-layer graphene according to claim 1, it is characterised in that:
(2) step adopt acetone to clean;
(3) step adopt centrifugal separation the suspension liquid that (1) step is obtained is carried out solid-liquid separation;
Temperature in (4) step 1 is 80 degrees Celsius, 240 minutes time of drying.
3. according to the preparation method of a kind of multi-layer graphene according to claim 1, it is characterised in that:
(2) step adopt methyl alcohol to clean;
(3) step adopt centrifugal separation the suspension liquid that (1) step is obtained is carried out solid-liquid separation;
Temperature in (4) step 1 is 90 degrees Celsius, 240 minutes time of drying.
4. according to the preparation method of a kind of multi-layer graphene according to claim 1, it is characterised in that:
(2) step adopt ethanol to clean;
(3) step adopt centrifugal separation the suspension liquid that (1) step is obtained is carried out solid-liquid separation;
Temperature in (4) step 1 is 110 degrees Celsius, 240 minutes time of drying.
5. according to the preparation method of a kind of multi-layer graphene according to claim 1, it is characterised in that:
(2) step adopt ethanol to clean;
(3) step adopt centrifugal separation the suspension liquid that (1) step is obtained is carried out solid-liquid separation;
Temperature in (4) step 1 is 120 degrees Celsius, 240 minutes time of drying.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106744895A (en) * | 2016-12-28 | 2017-05-31 | 江苏中亚新材料股份有限公司 | A kind of preparation method of high-purity multi-layer graphene |
| CN108545724A (en) * | 2018-07-23 | 2018-09-18 | 山东玉皇新能源科技有限公司 | Graphene and its production method, purposes and battery |
| WO2018187921A1 (en) * | 2017-04-11 | 2018-10-18 | 深圳市佩成科技有限责任公司 | Improved preparation method for graphene oxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102145887A (en) * | 2011-05-18 | 2011-08-10 | 中国科学院长春应用化学研究所 | Method for preparing and purifying graphene oxide |
| CN102167314A (en) * | 2011-05-23 | 2011-08-31 | 浙江大学 | Method for preparing graphene |
| CN102765716A (en) * | 2012-07-17 | 2012-11-07 | 上海大学 | Preparation method of graphene |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102145887A (en) * | 2011-05-18 | 2011-08-10 | 中国科学院长春应用化学研究所 | Method for preparing and purifying graphene oxide |
| CN102167314A (en) * | 2011-05-23 | 2011-08-31 | 浙江大学 | Method for preparing graphene |
| CN102765716A (en) * | 2012-07-17 | 2012-11-07 | 上海大学 | Preparation method of graphene |
Non-Patent Citations (3)
| Title |
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| BIHE YUAN ET AL.: "A facile approach to prepare graphene via solvothermal reduction of graphite oxide", 《MATERIALS RESEARCH BULLETIN》 * |
| C. NETHRAVATHI ET AL.: "Chemically modified graphene sheets produced by the solvothermal reduction of colloidal dispersions of graphite oxide", 《CARBON》 * |
| 何媛等: "基于天然石墨溶剂热法制备石墨烯及表征", 《非金属矿》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106744895A (en) * | 2016-12-28 | 2017-05-31 | 江苏中亚新材料股份有限公司 | A kind of preparation method of high-purity multi-layer graphene |
| WO2018187921A1 (en) * | 2017-04-11 | 2018-10-18 | 深圳市佩成科技有限责任公司 | Improved preparation method for graphene oxide |
| CN108545724A (en) * | 2018-07-23 | 2018-09-18 | 山东玉皇新能源科技有限公司 | Graphene and its production method, purposes and battery |
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