CN103991868B - A kind of preparation method of Graphene - Google Patents
A kind of preparation method of Graphene Download PDFInfo
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- CN103991868B CN103991868B CN201410260297.5A CN201410260297A CN103991868B CN 103991868 B CN103991868 B CN 103991868B CN 201410260297 A CN201410260297 A CN 201410260297A CN 103991868 B CN103991868 B CN 103991868B
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Abstract
The present invention relates to grapheme material preparing technical field, provide a kind of preparation method of Graphene, with expanded graphite, expansible black lead, high orientation graphite, one or more mixture in thermo-cracking graphite and/or crystalline flake graphite is raw material, using carboxylating agents such as the mixtures of one or more in citric acid and/or oxalic acid and carboxylic acid derivative thereof as intercalation reagent, particle diameter is controlled by raw materials pretreatment, wet ball grinding makes graphite thinning stripping under the special adsorption of carboxylating agent change carboxylation Graphene into, it is highly purified Graphene that microwave heating quick decarboxylation carboxylation Graphene is turned peels off.The present invention has that lower cost for material, manufacturing process are simple, environmental protection, be convenient to the feature of large-scale production.
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 prepared in 2004 first by the people such as An Deliegaimu (AndreK.Geim) of Univ Manchester UK, and the character of its uniqueness makes it be widely used in increasing industry.Such as, the tensile strength of Graphene up to 125GPa, Young's modulus reaches 1.1TPa, theoretical specific surface area can reach 2630m
2/ g, room temperature thermal conductivity are about 5000W/mK etc., make it possess the prospect applied as thermally conductive material; And single-layer graphene highly transparent, only absorbs the visible ray of 2.3%, also possesses the condition of application in illumination optical field.Therefore, require higher field of LED illumination in thermal conductivity, Graphene applies the heat sink material as excellent performance gradually.
But the manufacturing cost of Graphene remains high and directly limit its generally use in field of LED illumination, causes the cost pressure of LED illumination excessive.The method of current production 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 prepares the simplest directly method of Graphene, and preparation cost is low, sample quality is high, the Graphene size obtained can reach 100 μm, but this method yields poorly and uncontrollable, industrialization and large-scale production requirement can not be met, and it is more difficult to find single-layer graphene from the thick-layer of sheet, also there is a little glue stain in sample simultaneously, surface clearness is not high, limit its Application Areas, chemical Vapor deposition process can prepare high quality, large-area Graphene, but conventional substrate material monocrystalline nickel is expensive, and complex manufacturing, manufacturing cost decline difficulty is large, liquid phase stripping method needs to use poisonous and solvent that is 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 is 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, makes its lattice defect more thus affects use properties.Therefore, for promoting grapheme material in the popularization and application of field of LED illumination, 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 manufactures, and provides 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.
Content of the present invention is:
A preparation method for Graphene, using natural graphite as raw material, using carboxylating agent as intercalation reagent, comprises following process:
The first step, pre-treatment of raw material: first respectively by graphite, carboxylating agent grinding, sieve, to obtain median size be the powdered graphite of 200 ~ 500 μm and median size is 50 ~ 300 μm of carboxylating agent powder.Ball milling can make material surface area larger by micronized particles, augmenting response contact surface; The uniform particles that can make raw material of sieving is consistent, ensures mixed effect.
Prepared by second step, carboxylation Graphene: take powdered graphite and carboxylating agent powder according to weight proportion 1 ︰ 1 ~ 1 ︰ 2, be transferred in ball grinder, add deionized water as mixed solvent, add abrading-ball, arranging double planetary drum's speed of rotation is 300 ~ 1000rpm, ball milling 12 ~ 36h, obtains carboxylation Graphene dirty solution.In the process of ball milling, the shearing force of abrading-ball constantly makes graphite thinning and peel off and produce Graphene, phase mutual friction generate energy between abrading-ball thus make the surface of Graphene be in hot conditions, in addition there is oxygen in atmosphere, Graphene generation high temperature oxidation is changed to graphene oxide, graphene oxide is carboxylation agent and modifies under acidic high-temperature environment, finally become carboxylation Graphene, the continuous embedding of carboxylating agent produces intercalation effect, can accelerate the stripping between graphene layer further, final graphite all changes carboxylation Graphene into.
3rd step, the thick product of carboxylation Graphene are purified: carry out centrifugal successively by the carboxylation Graphene dirty solution prepared by second step, get supernatant liquid filtering, the solid filtered with deionized water wash is to neutral, then the solid of gained be placed in vacuum drying oven with the temperature drying 2 ~ 5h of 80 ~ 100 DEG C, be ground to Powdered, obtain the thick product of carboxylation Graphene.
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, microwave heating 5 ~ 10min, can prepare high purity graphite alkene product.Under heating condition, the carboxyl being in carboxylation graphene edge is removed by pyrolytic decomposition, and carboxylation Graphene is in the process of decarboxylation, and interfloor distance expands further, and finally thinning and stripping forms Graphene.
Preferably, described microwave heating power is 500 ~ 1000W.Microwave power arranges too low, and reaction is not thorough, length consuming time; Microwave power arranges too high, energy consumption can be caused to increase, waste energy, so microwave heating power setting is 500 ~ 1000W not only can ensure reaction effect but also achieve 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, without the need to extra process and processing, and low raw-material cost.
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 is very extensive, low cost of manufacture, and unreacted reactant can decompose and be pulled away in the process of microwave heating, can not have an impact 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, be convenient to large-scale production.
The invention has the beneficial effects as follows:
1, manufacturing process is simple; Graphene is prepared with the method for microwave heating method process carboxylation Graphene; raw materials pretreatment is that grinding is sieved; the preparation of carboxylation Graphene uses ball-milling technology; the decarboxylation of carboxylation Graphene adopts microwave heating; process step is few, and process control technology is ripe, thus method of the present invention has the operability of large-scale production in manufacture operability.
2, with low cost, in material, with natural graphites such as expanded graphite, expansible black lead, high orientation graphite, thermo-cracking graphite and crystalline flake graphites for raw material, using citric acid, oxalic acid and carboxy derivatives as carboxylating agent, source is very extensive, cheap; In equipment, required equipment is conventional equipment, invests little, simple to operate, thus method of the present invention has the feasibility of large-scale production in cost control.
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, the moisture that be can be implemented in intercalation by microwave heating is overflowed in high temperature environments, thus the product that on application prepared by method of the present invention has huge application prospect.
4, peel off reagent using carboxylating agent as intercalation in technique environmental protection, process, without chemical toxicity, the resultant product Sum decomposition product in its preparation process is very friendly to environment, and whole process is green production, meets the theme of environmental protection.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of the preparation method of a kind of Graphene of the present invention.
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 the citric acid powder obtaining median size to be respectively 200 μm of expanded graphite powder and median size be 300 μm.
(2) the preparation of carboxylation Graphene: take 20g expanded graphite and put in planetary ball mill together with 30g citric acid, add zirconium oxide balls, grinding 24h, rotating speed is 500rpm.Carboxylation Graphene mixed solution is obtained after ball milling terminates.
(3) the thick product of carboxylation Graphene is purified: the carboxylation Graphene mixed solution obtained in is (2) carried out centrifugal 30 minutes, supernatant liquor is collected, filter, with deionized water repeatedly clean to pH be 7, last in vacuum drying oven with the dry 5h of the temperature of 80 DEG C, obtain the thick product of carboxylation Graphene.
(4) the decarboxylation of carboxylation Graphene microwave fast heating is peeled off: the microwave reactor that the thick product of carboxylation Graphene obtained in (3) puts into 750W is heated 8min, and removing is adsorbed on the carboxylate group of graphene edge, obtains highly purified Graphene.
Embodiment 2
(1) raw materials pretreatment: ball milling sieves and obtains median size to be respectively high orientation graphite, thermo-cracking graphite mixed powder and the median size of 500 μm the be oxalic acid powder of 50 μm.
(2) the preparation of carboxylation Graphene: take 25g expanded graphite and put in planetary ball mill together with 25g citric acid, adds aluminum oxide abrading-ball, silicon nitride abrading-ball as abrading-ball, and grinding 36h, rotating speed is 300rpm.Carboxylation Graphene mixed solution is obtained after ball milling terminates.
(3) the thick product of carboxylation Graphene is purified: the carboxylation Graphene mixed solution obtained in is (2) carried out centrifugal 30 minutes, supernatant liquor is collected, filter, with deionized water repeatedly clean to pH be 7, last in vacuum drying oven with the dry 2h of the temperature of 100 DEG C, obtain the thick product of carboxylation Graphene.
(4) the decarboxylation of carboxylation Graphene microwave fast heating is peeled off: the microwave reactor that the thick product of carboxylation Graphene obtained in (3) puts into 600W is heated 10min, and removing is adsorbed on the carboxylate group of graphene edge, obtains highly purified Graphene.
Embodiment 3
(1) raw materials pretreatment: ball milling sieves and obtains median size to be respectively expanded graphite, thermo-cracking graphite mixed powder and the median size of 400 μm be oxalic acid, the citric acid mixed powder of 200 μm.
(2) the preparation of carboxylation Graphene: take 25g expanded graphite, thermo-cracking graphite mixed powder is put in planetary ball mill together with 50g oxalic acid, citric acid mixed powder, adds steel ball, agate abrading-ball as abrading-ball, and grinding 12h, rotating speed is 1000pm.Carboxylation Graphene mixed solution is obtained after ball milling terminates.
(3) the thick product of carboxylation Graphene is purified: the carboxylation Graphene mixed solution obtained in is (2) carried out centrifugal 30 minutes, supernatant liquor is collected, filter, with deionized water repeatedly clean to pH be 7, last in vacuum drying oven with the dry 4h of the temperature of 90 DEG C, obtain the thick product of carboxylation Graphene.
(4) the decarboxylation of carboxylation Graphene microwave fast heating is peeled off: the microwave reactor that the thick product of carboxylation Graphene obtained in (3) puts into 1000W is heated 5min, and removing is adsorbed on the carboxylate group of 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 done appropriate adaptation or amendment, all should within protection scope of the present invention.
Claims (4)
1. a preparation method for Graphene, is characterized in that, comprises following process:
The first step, pre-treatment of raw material: first respectively by graphite, carboxylating agent grinding, sieve, to obtain median size be the powdered graphite of 200 ~ 500 μm and median size is 50 ~ 300 μm of carboxylating agent powder;
Prepared by second step, carboxylation Graphene: take powdered graphite and carboxylating agent powder according to weight proportion 1 ︰ 1 ~ 1 ︰ 2, be transferred in ball grinder, add deionized water as mixed solvent, add abrading-ball, arranging double planetary drum's speed of rotation is 300 ~ 1000rpm, ball milling 12 ~ 36h, obtains carboxylation Graphene dirty solution;
3rd step, the thick product of carboxylation Graphene are purified: carry out centrifugal successively by the carboxylation Graphene dirty solution prepared by second step, get supernatant liquid filtering, the solid filtered with deionized water repetitive scrubbing is to neutral, then the solid of gained be placed in vacuum drying oven with the temperature drying 2 ~ 5h of 80 ~ 100 DEG C, be ground to Powdered, obtain the thick product of carboxylation Graphene;
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, microwave heating 5 ~ 10min, can prepare high purity graphite alkene product; Described microwave heating power is 500 ~ 1000W.
2. the preparation method of a kind of Graphene according to claim 1, 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.
3. 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.
4. the preparation method of a kind of Graphene according to claim 3, 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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| 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 |
| CN107734722B (en) * | 2015-12-31 | 2021-04-06 | 白德旭 | Graphene heating sheet and preparation method thereof |
| US9764955B2 (en) | 2016-01-19 | 2017-09-19 | King Abdulaziz University | Method for producing graphene with a controllable number of layers |
| 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 |
| CN110104641B (en) * | 2019-05-05 | 2021-03-16 | 华北电力大学 | Preparation method and application of foamy three-dimensional graphene oxide |
| 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 |
| 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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