CN105905889A - Method for producing graphene through high pressure hydrothermal expansion method - Google Patents
Method for producing graphene through high pressure hydrothermal expansion method Download PDFInfo
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- CN105905889A CN105905889A CN201610393191.1A CN201610393191A CN105905889A CN 105905889 A CN105905889 A CN 105905889A CN 201610393191 A CN201610393191 A CN 201610393191A CN 105905889 A CN105905889 A CN 105905889A
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- graphite powder
- graphene
- ammonium salt
- quaternary ammonium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/02—Single layer graphene
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/30—Purity
Abstract
The invention discloses a method for producing graphene through a high pressure hydrothermal expansion method. The method is characterized by comprising the following processes of adopting crystalline flake graphite powder with the diameter ranging from 100 microns to 500 microns as the raw material in a high pressure reaction kettle; adding deionized water; conducting a reaction for 0.1-30 hours at the constant temperature ranging from 100 DEG C to 300 DEG C; then spraying the crystalline flake graphite powder and the deionized water into a collector through a high pressure nozzle; after the materials are cooled, conducting graphene peeling on the crystalline flake graphite powder; then conducting centrifugal separation and frozen drying on peeled graphene, so that graphene in the powder form is obtained, wherein the mass ratio of the crystalline flake graphite powder to the deionized water is 1: (0.1-5). When the method is adopted for producing graphene, no pollution is caused; the method is environmentally friendly and a green production method.
Description
Technical field
Present invention relates particularly to a kind of method that water under high pressure dilatometry manufactures Graphene, belong to new carbon manufacturing technology field.
Background technology
Graphene comes out the only more than ten years, is a kind of hexagonal structure, the former molecular new carbon of monolayer carbon.Its conductivity reaches
One of three percentages of the light velocity, are 10 times of copper, and hardness is more than 100 times of iron and steel, and heat conductivility exceedes copper.Graphene molecules is tied
Structure is more stable, and excellent physicochemical property determines Graphene and has wide practical use, it has also become new carbon research in the world
Focus and emphasis.
Preparing the traditional method of Graphene is with crystalline flake graphite as raw material, with concentrated sulphuric acid, nitric acid, perchloric acid, acetic acid, Gao Meng
Acid potassium, hydrogen peroxide, sodium nitrate, potassium hyperchlorate etc. are made intercalation oxidant and are prepared graphite oxide, through high-temperature process, and ultrasonic stripping,
Obtain graphene oxide.Again with the strong reductant redox graphene such as hydrazine hydrate, sodium borohydride, obtain Graphene.These methods
Shortcoming is seriously polluted, and after graphite is oxidized, moieties structure is damaged.After sodium borohydride reduction, part Graphene is the most not
The intrinsic physicochemical property of Graphene can be replied.Response time is long, complex procedures.Traditional method is almost difficult to industrialized mass production.
Summary of the invention
It is an object of the invention to provide a kind of method that water under high pressure dilatometry manufactures Graphene, the method specifically uses following work
Skill:
In autoclave, with the crystalline graphite powder of 100-500 micron as raw material, add deionized water, at 100-300 DEG C
Isothermal reaction 0.1-30 hour, then sprays in catcher by high-pressure nozzle, after cooling by crystalline graphite powder and deionized water
Crystalline graphite powder is carried out the stripping that graphite is dilute, diluter being centrifuged of the graphite peeled off is separated and obtain powder stone after lyophilization
Ink alkene.Crystalline graphite powder is preferably 1 with the mass ratio of deionized water: 0.1-5.Phosphorus content >=99 mass % in crystalline graphite powder.
In the present invention, use deionized water as the intercalator of graphite, carry out intercalation at high temperature under high pressure, then by squama
Sheet graphite powder is sprayed by high-pressure nozzle together with deionized water, and due to gasification and the instantaneous decompression of water, deionized water occurs
Gasification, volume drastically expands, and expands the spacing of graphite linings, makes the Van der Waals force of graphite layers be preferably minimized or release, then
Graphite is carried out the stripping of Graphene again.Due to intercalation and the physical expansion of water, the interlamellar spacing of graphite expands several ten times larger, makes
The efficiency peeling off Graphene is greatly improved, and the Graphene peeled off keeps intrinsic physicochemical property and feature, becomes high purity graphite alkene and produces
Product.Water is the raw material of environmental protection, produces Graphene by the present invention and does not pollute, environmental friendliness, is a kind of Green production method.
Further, described crystalline graphite powder is the crystalline graphite powder through peracid intercalation；And in autoclave, it was also added with for three seasons
Ammonium salt emulsifying agent, three quaternary ammonium salt emulsifiers are 1-30: 100 with the mass ratio of crystalline graphite powder.Described three quaternary ammonium salt emulsifiers are preferred
For citric triester-triquat, maleic rosin three quaternary ammonium salt or double lauryl amine polyoxyethylene ether three quaternary ammonium salt.To scale stone
Ink carries out acid intercalation at present, and one uses concentrated sulphuric acid, concentrated nitric acid that crystalline graphite powder is carried out intercalation, and technology is the most ripe, energy
Enough meeting the needs of the application, detailed technical scheme does not repeats them here.
Three quaternary ammonium salt emulsifiers belong to cation, are positive charge through the electric charge of the graphite layers of the crystalline graphite powder of peracid intercalation, due to
The electrostatic repulsion of identical charges, makes graphite layers adhesion reduce, combines with the pressure for vaporization of high-temperature high pressure water, can make
The Van der Waals force of interlayer is preferably minimized or eliminates.Cationic emulsifier can reduce the surface tension of water, makes water enter hydrophobic graphite
The resistance degraded of interlayer, shortens the response time of water cutting layer.
For making the stripping that graphite is dilute more smooth, stripping preferably employs ultrasonic stripping method or crystalline graphite powder is entered by high shear stripping method
Row is peeled off.
The form the few-layer graphene that the employing present invention may separate out the number of plies≤5 layer is dilute dilute with mono-layer graphite.In separation process obtained by many
Layer graphite flake can return to repeatedly peel off 3-4 time in stripping machine, and last remaining Multi-layer graphite sheet can be again introduced into new graphite powder
To the raw material that autoclave is dilute as producing graphite.
Detailed description of the invention
Embodiment 1
Selection phosphorus content >=99 mass %, granularity are the crystalline flake graphite 200kg of 100-150 micron, and deionized water 20kg stirs
Pump in autoclave after mixing uniformly, heat to 180 DEG C, constant temperature 2h, carry out water intercalation.Open high-pressure nozzle
Valve, is sprayed on the mixture of crystalline graphite powder and deionized water in catcher；After cooling, by the scale through water intercalation
Graphite powder is pumped directly in ultrasonic stripping still stripping Graphene, after ultrasonic stripping 2h, isolates the widow of the number of plies≤5 layer with centrifuge
Layer graphene and single-layer graphene, remaining Multi-layer graphite sheet returns again to repeatedly peel off 3-4 time in ultrasonic stripping still, finally remaining
Multi-layer graphite sheet and new crystalline graphite powder enter back in autoclave and process.
After the graphene aqueous solution ultrafiltration that centrifuge separates separates and be freeze-dried, obtain powder high purity graphite alkene product.
Embodiment 2
The crystalline graphite powder 200kg through peracid intercalation selecting phosphorus content >=99 mass %, granularity to be 300-400 micron, goes
Ionized water 200kg, maleic rosin three quaternary ammonium salt emulsifier 2kg, pump into autoclave, be heated to 220 DEG C after mix homogeneously,
Isothermal reaction 10h, opens high-pressure nozzle valve, is sprayed in catcher by the mixture of crystalline graphite powder and deionized water；Treat cold
But after, the crystalline graphite powder through water intercalation is pumped directly in ultrasonic stripping still stripping Graphene, after ultrasonic stripping 2h, uses
Form the few-layer graphene alkene and the single-layer graphene of the number of plies≤5 layer isolated by centrifuge, and remaining Multi-layer graphite sheet returns again to ultrasonic stripping still
In repeatedly peel off 3-4 time, last remaining Multi-layer graphite sheet and new crystalline graphite powder enter back in autoclave and process.
Form the few-layer graphene alkene and the single-layer graphene of isolated for the centrifuge number of plies≤5 layer are carried out lyophilization, obtains high-purity stone
Ink alkene powder.
Under the expansion of steam pressure, owing to pressure moment reduces, the inside of crystalline graphite powder expands reaction.Horse
Carry out Colophonium three quaternary ammonium salt emulsifier and belong to cationic substance, and through the electric charge of the graphite layers of the crystalline flake graphite of peracid intercalation be positive charge；
Due to the electrostatic repulsion of identical charges, make graphite layers adhesion reduce, combine with the pressure for vaporization of high-temperature high pressure water,
The Van der Waals force that can make interlayer is preferably minimized or eliminates.
Embodiment 3
The crystalline graphite powder 200kg through peracid intercalation selecting phosphorus content >=99 mass %, granularity to be 400-500 micron, goes
Ionized water 1000kg, double lauryl amine polyoxyethylene ether three quaternary ammonium salt emulsifier 60kg, pump into autoclave after mix homogeneously,
It is heated to 300 DEG C, isothermal reaction 30h, opens high-pressure nozzle valve, the mixture of crystalline graphite powder and deionized water is sprayed on receipts
In storage；After cooling, the crystalline graphite powder through water intercalation is pumped directly in ultrasonic stripping still stripping Graphene, ultrasonic
After peeling off 2h, isolate form the few-layer graphene alkene and the single-layer graphene of the number of plies≤5 layer with centrifuge.
Form the few-layer graphene alkene and the single-layer graphene of isolated for the centrifuge number of plies≤5 layer are carried out lyophilization, obtains high-purity stone
Ink alkene powder.
Under the expansion of steam pressure, owing to pressure moment reduces, the inside of crystalline graphite powder expands reaction.Double
Lauryl amine polyoxyethylene ether three quaternary ammonium salt emulsifier belongs to cationic substance, and the graphite layers of the crystalline flake graphite through peracid intercalation
Electric charge be positive charge；Due to the electrostatic repulsion of identical charges, graphite layers adhesion is made to reduce, with high-temperature high pressure water
Pressure for vaporization combines, and the Van der Waals force of interlayer can be made to be preferably minimized or eliminate.
Claims (6)
1. the method that a water under high pressure dilatometry manufactures Graphene, it is characterised in that use following technique:
In autoclave, with the crystalline graphite powder of 100-500 micron as raw material, add deionized water, at 100-300 DEG C
Isothermal reaction 0.1-30 hour, then sprays in catcher by high-pressure nozzle, after cooling by crystalline graphite powder and deionized water
Crystalline graphite powder is carried out the stripping that graphite is dilute, diluter being centrifuged of the graphite peeled off is separated and obtain powder stone after lyophilization
Ink alkene.
Method the most according to claim 1, it is characterised in that crystalline graphite powder is 1 with the mass ratio of deionized water:
0.1-5。
Method the most according to claim 1, it is characterised in that described crystalline graphite powder is the crystalline flake graphite through peracid intercalation
Powder；And in autoclave, it being also added with three quaternary ammonium salt emulsifiers, three quaternary ammonium salt emulsifiers with the mass ratio of crystalline graphite powder are
1-30∶100。
Method the most according to claim 3, it is characterised in that described three quaternary ammonium salt emulsifiers are citric acid three ester three quaternary ammonium
Salt, maleic rosin three quaternary ammonium salt or double lauryl amine polyoxyethylene ether three quaternary ammonium salt.
Method the most according to claim 1, it is characterised in that the stripping that graphite is dilute uses ultrasonic stripping method or high shear stripping
Carry out from method.
Method the most according to claim 1, it is characterised in that phosphorus content >=99 mass % in crystalline graphite powder.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106744881A (en) * | 2016-12-27 | 2017-05-31 | 成都新柯力化工科技有限公司 | A kind of method that utilization ultrasonic continuous prepare Graphene |
| CN108751792A (en) * | 2018-05-12 | 2018-11-06 | 深圳莱必德科技股份有限公司 | A kind of graphene heat dissipation plastic particles manufacturing method |
| CN110078067A (en) * | 2019-06-13 | 2019-08-02 | 广东凯金新能源科技股份有限公司 | A kind of preparation method for the graphite cathode material that end face structure is controllable |
| CN114956072A (en) * | 2022-06-08 | 2022-08-30 | 中国科学院过程工程研究所 | Method for expanding natural graphite spherical tailing by steam pressure |
| CN116495727A (en) * | 2023-05-19 | 2023-07-28 | 烟台大学 | Preparation method and application of expanded graphene material by using popcorn machine |
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| CN105293482A (en) * | 2015-12-01 | 2016-02-03 | 张扬威 | Solvothermal stripping preparation method of graphene |
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| JP2012131691A (en) * | 2010-11-29 | 2012-07-12 | Sekisui Chem Co Ltd | Expanded graphite and method for producing the same |
| CN102491314A (en) * | 2011-11-24 | 2012-06-13 | 中国科学院化学研究所 | Method for preparing graphene |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106744881A (en) * | 2016-12-27 | 2017-05-31 | 成都新柯力化工科技有限公司 | A kind of method that utilization ultrasonic continuous prepare Graphene |
| CN108751792A (en) * | 2018-05-12 | 2018-11-06 | 深圳莱必德科技股份有限公司 | A kind of graphene heat dissipation plastic particles manufacturing method |
| CN110078067A (en) * | 2019-06-13 | 2019-08-02 | 广东凯金新能源科技股份有限公司 | A kind of preparation method for the graphite cathode material that end face structure is controllable |
| CN114956072A (en) * | 2022-06-08 | 2022-08-30 | 中国科学院过程工程研究所 | Method for expanding natural graphite spherical tailing by steam pressure |
| CN116495727A (en) * | 2023-05-19 | 2023-07-28 | 烟台大学 | Preparation method and application of expanded graphene material by using popcorn machine |
| CN116495727B (en) * | 2023-05-19 | 2024-01-23 | 烟台大学 | Preparation method and application of expanded graphene material by using popcorn machine |
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Application publication date: 20160831 |