CN103991868A - Preparation method of graphene - Google Patents
Preparation method of graphene Download PDFInfo
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- CN103991868A CN103991868A CN201410260297.5A CN201410260297A CN103991868A CN 103991868 A CN103991868 A CN 103991868A CN 201410260297 A CN201410260297 A CN 201410260297A CN 103991868 A CN103991868 A CN 103991868A
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Abstract
The invention relates to the technical field of preparation of graphene materials and provides a preparation method of graphene. The preparation method comprises the following steps: by taking one or more than one of expanded graphite, expandable graphite, high-oriented graphite, thermally cracked graphite and/or crystalline flake graphite as raw materials and one or more than one of carboxylation agents (including citric acid and/or oxalic acid and carboxylic acid derivatives thereof) as an intercalating reagent, carrying out pre-treatment on the raw materials to control the grain size; ball-milling by a wet process so that graphite is thinned, stripped and converted into carboxylated graphene under the intercalating effect of the carboxylation agent; and carrying out microwave heating to quickly decarboxylate the carboxylated graphene so that the carboxylated graphene is converted and stripped into high-purity graphene. The graphene provided by the invention has the characteristics of low material cost, simple manufacturing process and environmental friendliness and can be put into large-scale production conveniently.
Description
Technical field
The present invention relates to grapheme material preparing technical field, particularly a kind of preparation method of Graphene.
Background technology
Graphene is by the people such as An Deliegaimu (Andre K. Geim) preparation first in 2004 of Univ Manchester UK, and its unique character is widely used it in increasing industry.For example, the tensile strength of Graphene up to 125 GPa, Young's modulus reach 1.1 TPa, theoretical specific surface area can reach 2630 m
2/ g, room temperature thermal conductivity are about 5000 W/mK etc., make it possess the prospect as thermally conductive material application; And single-layer graphene highly transparent, only absorbs 2.3% visible ray, also possesses the condition of application in illumination optical field.Therefore, in thermal conductivity, require higher LED lighting field, Graphene is applied the heat sink material as excellent performance gradually.
But the manufacturing cost of Graphene remains high and directly limited its generally use at LED lighting field, cause the cost pressure of LED illumination excessive.The method of producing at present Graphene mainly contains micromechanics partition method, chemical Vapor deposition process, liquid phase stripping method, SiC epitaxial growth method, these are several for oxidation reduction process, micromechanics partition method is to prepare the simplest directly method of Graphene, and preparation cost is low, sample quality is high, the Graphene size obtaining can reach 100 μ m, but this method yields poorly and is uncontrollable, can not meet industrialization and large-scale production requirement, and it is more difficult from large stretch of thick-layer, to find single-layer graphene, in sample, also there is a little glue stain simultaneously, surface clearness is not high, limited its Application Areas, chemical Vapor deposition process can be prepared high quality, large-area Graphene, but conventional substrate material monocrystalline nickel is expensive, and complex manufacturing, and manufacturing cost decline difficulty is large, liquid phase stripping method need to be used poisonous and solvent highly corrosive, does not meet safety growth and environmental requirement, SiC epitaxial growth method can obtain individual layer (or multilayer), large-area Graphene, but preparation condition is harsh, needs high temperature and ultrahigh vacuum(HHV), and SiC material expensive, cannot large-scale production, graphene oxide reduction method makes the electronic structure of Graphene and perfection of crystal be subject to strong oxidizer effect and produces serious destruction, thereby makes the more use properties that affects of its lattice defect.Therefore, be to promote grapheme material in the popularization and application of LED lighting field, need to find the high purity graphite alkene preparation method that a kind of lower cost for material, manufacturing process are simple, be convenient to large-scale production.
Summary of the invention
The object of the invention is to overcome the problem of current graphene preparation method on mass-producing is manufactured, and the high purity graphite alkene preparation method that a kind of lower cost for material, manufacturing process are simple, be convenient to large-scale production is provided.
Content of the present invention is:
A preparation method for Graphene, usings natural graphite as raw material, usings carboxylating agent as intercalation reagent, comprises following process:
The first step, pre-treatment of raw material: first respectively graphite, carboxylating agent are ground, sieved, obtaining powdered graphite and median size that median size is 200～500 μ m is 50～300 μ m carboxylating agent powder.Ball milling can make stock chart area larger by refinement particle, augmenting response contact surface; Sieve and can make the uniform particles of raw material consistent, guarantee mixed effect.
Second step, the preparation of carboxylation Graphene: according to weight proportion, 1 ︰ 1～1 ︰ 2 takes powdered graphite and carboxylating agent powder, be transferred in ball grinder, add deionized water as mixed solvent, add abrading-ball, it is 300～1000 rpm that double-planet formula drum's speed of rotation is set, ball milling 12～36 h, obtain carboxylation Graphene dirty solution.In the process of ball milling, the shearing force of abrading-ball constantly makes graphite attenuate and peels off generation Graphene, between abrading-ball, thereby phase mutual friction generate energy makes the surface of Graphene in hot conditions, in addition in air, there is oxygen, Graphene generation high temperature oxidation is changed to graphene oxide, graphene oxide is carboxylation agent and modifies under acid hot environment, finally become carboxylation Graphene, the continuous embedding of carboxylating agent produces intercalation effect, can further accelerate peeling off between graphene layer, final graphite all changes carboxylation Graphene into.
The 3rd step, the thick product of carboxylation Graphene are purified: the carboxylation Graphene dirty solution that second step is prepared carries out centrifugal successively, get supernatant liquid filtering, with deionized water wash filter solid to neutral, then the solid of gained be placed in vacuum drying oven with dry 2～5 h of the temperature of 80～100 ℃, be ground to Powderedly, obtain the thick product of carboxylation Graphene.
The 4th step, the decarboxylation of carboxylation Graphene microwave fast heating are peeled off: the thick product of carboxylation Graphene of the 3rd step gained is put into microwave container, and microwave heating 5～10min, can prepare high purity graphite alkene product.Under heating condition, in the carboxyl at carboxylation Graphene edge, by pyrolytic decomposition, removed, carboxylation Graphene is in the process of decarboxylation, and interfloor distance further expands, final attenuate and peel off formation Graphene.
Preferably, described microwave heating power is 500～1000 W.Microwave power arranges too low, reacts not thorough, length consuming time; Microwave power arranges too high, can cause energy consumption to increase, and wastes energy, so microwave heating power setting is 500～1000 W, not only can guarantee reaction effect but also realized less energy-consumption production.
Preferably, described graphite is one or more the mixture in expanded graphite, expansible black lead, high orientation graphite, thermo-cracking graphite and/or crystalline flake graphite.Expanded graphite, expansible black lead, high orientation graphite, thermo-cracking graphite and crystalline flake graphite source are very abundant, and without extra process and processing, raw materials cost is cheap.
Preferably, described carboxylating agent is one or more mixture of citric acid and/or oxalic acid and carboxylic acid derivative thereof.Citric acid, oxalic acid and carboxy derivatives source are very extensive, low cost of manufacture, and unreacted reactant can decompose and be pulled away in the process of microwave heating, can not exert an influence to the purity of the finished product.
Preferably, described abrading-ball is steel ball, agate abrading-ball, zirconium oxide balls, aluminum oxide abrading-ball or silicon nitride abrading-ball.The uniformity coefficient of different ball-milling mediums ball milling in the process of ball milling is different with the heat that ball milling produces, and can meet the mixing demand of different blended resultant, is convenient to large-scale production.
The invention has the beneficial effects as follows:
1, manufacturing process is simple; with microwave heating method, process the method for carboxylation Graphene and prepare Graphene; raw materials pretreatment is sieved for grinding; ball-milling technology is used in the preparation of carboxylation Graphene; the decarboxylation of carboxylation Graphene adopts microwave heating; process step is few, and process control technology is ripe, thereby in the method for the present invention in operability manufactured, has the operability of large-scale production.
2, with low cost, aspect material, the natural graphites such as expanded graphite, expansible black lead, high orientation graphite, thermo-cracking graphite and crystalline flake graphite of take are raw material, using citric acid, oxalic acid and carboxy derivatives as carboxylating agent, originate very extensive, cheap; Aspect equipment, required equipment is conventional equipment, invest little, simple to operate, thereby in cost control, method of the present invention has the feasibility of large-scale production.
3, product purity is high, pass through centrifugal method, can effectively remove in ball-milling reaction unreacted as solid impurities such as graphite, deionized water repetitive scrubbing can be removed and attach unreacted carboxylating agent on carboxylation Graphene, by microwave heating, can realize at the moisture of intercalation and overflowing under hot environment, thereby the product that on application prepared by method of the present invention has huge application prospect.
4, the carboxylating agent of usining in technique environmental protection, process is peeled off reagent as intercalation, and without chemical toxicity, the resultant product in its preparation process and degradation production are very friendly to environment, and whole process is green production, meets the theme of environmental protection.
Accompanying drawing explanation
Fig. 1 is the preparation method's of a kind of Graphene of the present invention process flow sheet.
Embodiment
Below in conjunction with accompanying drawing, specific embodiments of the invention are conducted further description:
Embodiment 1
A preparation method for Graphene, its technical process is as follows:
(1) raw materials pretreatment: ball milling sieves and obtains respectively median size is that 200 μ m expanded graphite powder and median size are the citric acid powder of 300 μ m.
(2) the preparation of carboxylation Graphene: take 20 g expanded graphites and put in planetary ball mill together with 30 g citric acids, add zirconium oxide balls, grind 24h, rotating speed is 500rpm.After finishing, ball milling obtains carboxylation Graphene mixed solution.
(3) the thick product of carboxylation Graphene is purified: the carboxylation Graphene mixed solution obtaining in is (2) carried out centrifugal 30 minutes, supernatant liquor is collected, is filtered, with deionized water repeatedly clean to pH be 7, finally in vacuum drying oven, the temperature with 80 ℃ is dried 5 h, obtains the thick product of carboxylation Graphene.
(4) the decarboxylation of carboxylation Graphene microwave fast heating is peeled off: the microwave reactor of the thick product of carboxylation Graphene obtaining in (3) being put into 750 W heats 8min, removes the carboxylation group that is adsorbed on Graphene edge, obtains highly purified Graphene.
Embodiment 2
(1) raw materials pretreatment: ball milling sieves and obtains respectively median size is that high orientation graphite, thermo-cracking graphite mixed powder and the median size of 500 μ m is the oxalic acid powder of 50 μ m.
(2) the preparation of carboxylation Graphene: take 25 g expanded graphites and put in planetary ball mill together with 25 g citric acids, add aluminum oxide abrading-ball, silicon nitride abrading-ball as abrading-ball, grind 36 h, rotating speed is 300rpm.After finishing, ball milling obtains carboxylation Graphene mixed solution.
(3) the thick product of carboxylation Graphene is purified: the carboxylation Graphene mixed solution obtaining in is (2) carried out centrifugal 30 minutes, supernatant liquor is collected, is filtered, with deionized water repeatedly clean to pH be 7, finally in vacuum drying oven, the temperature with 100 ℃ is dried 2 h, obtains the thick product of carboxylation Graphene.
(4) the decarboxylation of carboxylation Graphene microwave fast heating is peeled off: the microwave reactor of the thick product of carboxylation Graphene obtaining in (3) being put into 600 W heats 10 min, removes the carboxylation group that is adsorbed on Graphene edge, obtains highly purified Graphene.
Embodiment 3
(1) raw materials pretreatment: ball milling sieves and obtains respectively expanded graphite, thermo-cracking graphite mixed powder and the median size that median size is 400 μ m is oxalic acid, the citric acid mixed powder of 200 μ m.
(2) the preparation of carboxylation Graphene: take 25 g expanded graphites, thermo-cracking graphite mixed powder is put in planetary ball mill together with 50 g oxalic acid, citric acid mixed powder, adds steel ball, agate abrading-ball as abrading-ball, grind 12 h, rotating speed is 1000pm.After finishing, ball milling obtains carboxylation Graphene mixed solution.
(3) the thick product of carboxylation Graphene is purified: the carboxylation Graphene mixed solution obtaining in is (2) carried out centrifugal 30 minutes, supernatant liquor is collected, is filtered, with deionized water repeatedly clean to pH be 7, finally in vacuum drying oven, the temperature with 90 ℃ is dried 4h, obtains the thick product of carboxylation Graphene.
(4) the decarboxylation of carboxylation Graphene microwave fast heating is peeled off: the microwave reactor of the thick product of carboxylation Graphene obtaining in (3) being put into 1000W heats 5min, removes the carboxylation group that is adsorbed on Graphene edge, obtains highly purified Graphene.
Foregoing, is only preferred embodiment of the present invention, and not for limiting embodiment of the present invention, those skilled in the art are according to design of the present invention, and the appropriate adaptation of having done or modification, all should be within protection scope of the present invention.
Claims (5)
1. a preparation method for Graphene, is characterized in that, comprises following process:
The first step, pre-treatment of raw material: first respectively graphite, carboxylating agent are ground, sieved, obtaining powdered graphite and median size that median size is 200～500 μ m is 50～300 μ m carboxylating agent powder;
Second step, the preparation of carboxylation Graphene: according to weight proportion, 1 ︰ 1～1 ︰ 2 takes powdered graphite and carboxylating agent powder, be transferred in ball grinder, add deionized water as mixed solvent, add abrading-ball, it is 300～1000 rpm that double-planet formula drum's speed of rotation is set, ball milling 12～36 h, obtain carboxylation Graphene dirty solution;
The 3rd step, the thick product of carboxylation Graphene are purified: the carboxylation Graphene dirty solution that second step is prepared carries out centrifugal successively, get supernatant liquid filtering, with deionized water repetitive scrubbing filter solid to neutral, then the solid of gained be placed in vacuum drying oven with dry 2～5 h of the temperature of 80～100 ℃, be ground to Powderedly, obtain the thick product of carboxylation Graphene;
The 4th step, the decarboxylation of carboxylation Graphene microwave fast heating are peeled off: the thick product of carboxylation Graphene of the 3rd step gained is put into microwave container, and microwave heating 5～10 min, can prepare high purity graphite alkene product.
2. the preparation method of a kind of Graphene according to claim 1, is characterized in that: described microwave heating power is 500～1000 W.
3. according to claim 1 or 2 or the preparation method of described a kind of Graphene, it is characterized in that: described graphite is one or more the mixture in expanded graphite, expansible black lead, high orientation graphite, thermo-cracking graphite and/or crystalline flake graphite.
4. the preparation method of a kind of Graphene according to claim 1 and 2, is characterized in that: described carboxylating agent is one or more the mixture in citric acid and/or oxalic acid and carboxylic acid derivative thereof.
5. the preparation method of a kind of Graphene according to claim 4, is characterized in that: described abrading-ball is steel ball, agate abrading-ball, zirconium oxide balls, aluminum oxide abrading-ball or silicon nitride abrading-ball.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105506812A (en) * | 2015-12-31 | 2016-04-20 | 白德旭 | Graphene smart clothes |
| CN105800603A (en) * | 2016-04-22 | 2016-07-27 | 华侨大学 | Method for quickly preparing high-quality graphene |
| CN106145099A (en) * | 2016-07-01 | 2016-11-23 | 成都新柯力化工科技有限公司 | A kind of Graphene paste materials and preparation method thereof |
| CN106185889A (en) * | 2016-07-04 | 2016-12-07 | 苏州云舒新材料科技有限公司 | A kind of grapheme material and preparation method thereof |
| CN106554010A (en) * | 2015-09-25 | 2017-04-05 | 苏州烯时代石墨烯科技有限公司 | The method of preparation of industrialization big size graphene |
| US9764955B2 (en) | 2016-01-19 | 2017-09-19 | King Abdulaziz University | Method for producing graphene with a controllable number of layers |
| CN107930778A (en) * | 2017-10-30 | 2018-04-20 | 李文辉 | A kind of graphene physics peels off production method and the graphene produced |
| CN110104641A (en) * | 2019-05-05 | 2019-08-09 | 华北电力大学 | A kind of preparation method and application of foam-like 3 D stereo graphene oxide |
| CN113493200A (en) * | 2020-10-17 | 2021-10-12 | 苏州北美国际高级中学 | Preparation method of graphene oxide |
| CN114162815A (en) * | 2020-09-10 | 2022-03-11 | 中国石油化工股份有限公司 | Expandable graphite material, preparation method and application thereof |
| CN115285985A (en) * | 2022-10-10 | 2022-11-04 | 深圳华烯新材料有限公司 | Preparation method of carboxylated graphene and carboxylated graphene prepared by same |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106554010A (en) * | 2015-09-25 | 2017-04-05 | 苏州烯时代石墨烯科技有限公司 | The method of preparation of industrialization big size graphene |
| CN105506812A (en) * | 2015-12-31 | 2016-04-20 | 白德旭 | Graphene smart clothes |
| US9764955B2 (en) | 2016-01-19 | 2017-09-19 | King Abdulaziz University | Method for producing graphene with a controllable number of layers |
| CN105800603A (en) * | 2016-04-22 | 2016-07-27 | 华侨大学 | Method for quickly preparing high-quality graphene |
| CN105800603B (en) * | 2016-04-22 | 2018-01-09 | 华侨大学 | A kind of quick method for preparing high-quality graphene |
| CN106145099A (en) * | 2016-07-01 | 2016-11-23 | 成都新柯力化工科技有限公司 | A kind of Graphene paste materials and preparation method thereof |
| CN106185889A (en) * | 2016-07-04 | 2016-12-07 | 苏州云舒新材料科技有限公司 | A kind of grapheme material and preparation method thereof |
| CN107930778B (en) * | 2017-10-30 | 2024-03-22 | 李文辉 | Graphene physical stripping production method and produced graphene |
| CN107930778A (en) * | 2017-10-30 | 2018-04-20 | 李文辉 | A kind of graphene physics peels off production method and the graphene produced |
| CN110104641A (en) * | 2019-05-05 | 2019-08-09 | 华北电力大学 | A kind of preparation method and application of foam-like 3 D stereo graphene oxide |
| CN110104641B (en) * | 2019-05-05 | 2021-03-16 | 华北电力大学 | Preparation method and application of foamy three-dimensional graphene oxide |
| CN114162815A (en) * | 2020-09-10 | 2022-03-11 | 中国石油化工股份有限公司 | Expandable graphite material, preparation method and application thereof |
| CN114162815B (en) * | 2020-09-10 | 2023-03-10 | 中国石油化工股份有限公司 | Expandable graphite material, preparation method and application thereof |
| CN113493200A (en) * | 2020-10-17 | 2021-10-12 | 苏州北美国际高级中学 | Preparation method of graphene oxide |
| CN115285985A (en) * | 2022-10-10 | 2022-11-04 | 深圳华烯新材料有限公司 | Preparation method of carboxylated graphene and carboxylated graphene prepared by same |
| CN115285985B (en) * | 2022-10-10 | 2022-12-06 | 深圳华烯新材料有限公司 | Preparation method of carboxylated graphene and carboxylated graphene prepared by same |
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