CN105836734A - Rapid preparation method for high-quality graphene - Google Patents
Rapid preparation method for high-quality graphene Download PDFInfo
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- CN105836734A CN105836734A CN201610150020.6A CN201610150020A CN105836734A CN 105836734 A CN105836734 A CN 105836734A CN 201610150020 A CN201610150020 A CN 201610150020A CN 105836734 A CN105836734 A CN 105836734A
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- 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
- C01B2204/22—Electronic properties
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- 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
- C01B2204/32—Size or surface area
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- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The invention provides a rapid preparation method for high-quality graphene. The method comprises the following steps: adding graphite into a solution containing an intercalator and carrying out uniform mixing under stirring; then adding a peeling auxiliary agent and continuing ultrasonic treatment so as to allow graphite to be peeled; then carrying out washing until a pH value reaches 7.0; carrying out centrifugation to remove bottom insoluble substances so as to obtain graphene dispersion liquid; and drying the graphene dispersion liquid so as to obtain high-quality graphene powder. The method provided by the invention is simple, easy to operate, safe, environment-friendly and applicable to large-scale preparation of high-quality graphene; and the prepared graphene has a high peeling degree, a great specific surface area, few defects and high electric conductivity and thermal conductivity.
Description
Technical field
The invention belongs to technical field of graphene preparation, a kind of method relating to quick preparation high-quality Graphene.
Background technology
Graphene is the flake graphite material with one or several carbon atomic layer thickness that British scientist finds for 2004
Material.Graphene has high electron transfer rate because of the two dimensional crystal structure of its uniqueness, and is known mechanical strength
The highest material, has the most excellent electricity, mechanics, calorifics and magnetic performance, is the quite varied green wood of a kind of purposes
Material.Owing to having potential application prospect in various fields, therefore the basis of Graphene and applied research have become various countries' science
The focus of family's research.
At present, propose the preparation method of a lot of Graphene both at home and abroad, most typically with graphite as raw material, by oxidation
Intercalation obtains graphite oxide, then obtains Graphene through chemistry or thermal reduction method.Owing to using during preparing graphite oxide
Substantial amounts of strong oxidizer, makes the structure of graphite by considerable damage, although has repaired a part after reduction, but still has had a large amount of lacking
Fall into and exist, cause the heat conduction of gained Graphene and electric conductivity poor.Additionally, the dispersibility that Graphene is in the solution is poor, one
As concentration less than 3wt%.Subsequently, scientist proposes by the most ultrasonic, directly graphite is peeled off into Graphene, even if when peeling off
Being previously added intercalator, the charge stripping efficiency of graphite is the lowest, and splitting time is the longest.Sending out of Publication No. CN103253659A
Bright patent discloses a kind of method that ultrasound wave peels off preparing graphite alkene, uses the series compounds such as naphthalene as intercalator system
Standby Graphene, but used by it, intercalator is noxious substance, easily works the mischief human body, and gained graphene dispersing solution
Concentration relatively low (being up to 0.15mg/mL).The patent of invention of Publication No. CN103570012A discloses the system of a kind of Graphene
Preparation Method, first processes graphite with the acid solution of potassium permanganate, then adds and mix through ultrasonic with alkali or salt active substance
Process to obtain graphene dispersing solution.Owing to the acid solution of potassium permanganate has strong oxidizing property, graphite can be made oxidized, and follow-up place
Reason process does not has any reduction measure, and gained Graphene has certain oxygen-containing functional group, and defect also will be many.Therefore, it is led
Heat and electric conductivity are poor.
Summary of the invention
The purpose of the present invention fundamentally solves the problems referred to above, proposes a kind of technological process short, heat conduction and conducting electricity very well,
Pollution-free, that energy consumption the is low method quickly preparing high-quality Graphene.
The present invention is, by carbonate, graphite is carried out pre-intercalation, then adds stripping auxiliary agent, with the carbon of graphite layers
Hydrochlorate reacts, and produces substantial amounts of carbon dioxide, produces cooperative effect with ultrasonic cavitation, it is achieved the quick height of graphite
Effect is peeled off, and effectively reduces energy consumption, substantially reduces splitting time, improves charge stripping efficiency and the productivity of Graphene and quality.
The present invention is realized by the following technical programs, a kind of method of quick preparation high-quality Graphene, its
It is characterised by comprising the following steps:
(1) graphite powder is joined in the solution containing intercalator it is stirred；
(2) add stripping auxiliary agent, carry out supersound process simultaneously；
(3) the solvent washing used with step (1) solution is the most neutral, obtains Graphene and divide bottom centrifugal segregation after insoluble matter
Dissipate liquid；
(4) gained graphene dispersing solution is dried, obtains Graphene.
Described graphite powder includes crystalline flake graphite, blocky graphite or amorphous graphite, and particle diameter is 1-40 μm.
Described intercalator be the soluble carbonate salts such as sodium bicarbonate, sodium carbonate, potassium carbonate one or more.
The described solvent in the solution containing intercalator be deionized water, ethanol, acetone etc. one or more.
Described stripping auxiliary agent be sulphuric acid, hydrochloric acid, phosphoric acid, nitric acid, formic acid, acetic acid etc. one or more.
The mass ratio of described graphite powder, intercalator and stripping auxiliary agent is 1:0.1-0.3:0.2-0.6, and graphite powder is inserted with containing
The relative scale of layer agent solution is 1g:100-500mL.
Described stirring is to carry out at 50-120 DEG C, and mixing time is 1-3h.
Described ultrasonic power is 10-200 watt, and ultrasonic time is 1-15 minute.
Described Graphene specific surface area is 300-1310m2/ g, the average number of plies is 2-9 layer, and monolayer rate is 6-45%, flat
The most a size of 500nm-23 μm, powder resistivity is 60-100 μ Ω m.
The present invention compared with prior art has the advantages that
(1) reaction of ultrasonic cavitation and intercalator with stripping auxiliary agent is combined by the present invention, utilizes and inserts
Layer agent and stripping auxiliary agent, at the gas of the reaction in-situ release of graphite layers, form certain air pressure at interlayer, offset part layer
Between Van der Waals force, reduce peel resistance, improve peeling effect, the productivity of Graphene be more than 70%.Meanwhile, reduce ultrasonic
Power, frequency and time.On the one hand the noise pollution in cost and ultrasonic procedure is effectively reduced；The more important thing is, due to super
The reduction of acoustical power, frequency and time, decreases the defect in the Graphene after stripping, is conducive to preparation large scale high-quality stone
Ink alkene.
(2) this technique avoids the use of surfactant, effectively reduces the impurity such as metal ion in made Graphene
Content, ash be less than 0.1wt%, metal ion content be less than 50ppm, it is ensured that Graphene is at lithium ion battery, super capacitor
The application in the field such as device and catalyst.
(3) present invention can simultaneously output graphene powder and dispersion liquid, effectively solve Graphene high concentration in a solvent
Scattering problem, effectively solves the cost in high-quality Graphene scale preparation process, efficiency, asking of storing, transport and use
Topic.
(4) reagent used in the present invention is commercially available conventional reagent, cheap, environmentally safe, belongs to a kind of
Environmentally friendly high-quality graphene preparation technology.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope diagram sheet of the made Graphene of embodiment 3.
Detailed description of the invention
Below by way of instantiation, technical scheme is described.It should be understood that the present invention mention one or more
Step is not repelled and be there is also other method and steps before and after described combination step, or between these specifically mentioned steps also
May be inserted into other method and steps.Should also be understood that these examples are merely to illustrate the present invention rather than limit the present invention's
Scope.Except as otherwise noted, the numbering of various method steps is only the purpose differentiating various method steps, rather than for limit each method
Ordering or limit the present invention practical range, being altered or modified of its relativeness, without substantial technological content alteration
Under conditions of, when being also considered as the enforceable category of the present invention.
Embodiment 1
(1) crystalline flake graphite that 1g particle diameter is 20 μm is joined in the aqueous solution that 100mL contains 0.1g sodium carbonate, at 50 DEG C
Stirring 1h；
(2) add 0.2g hydrochloric acid, use 100 watts of power, ultrasonic 15 minutes.
(3) it is washed with deionized to neutrality, bottom centrifugal segregation, after insoluble matter, obtains graphene dispersing solution；
(4) gained graphene dispersing solution is dried, obtains Graphene.
Graphene productivity is 90%, and using physical adsorption appearance to record specific surface area is 657m2/ g, the average number of plies is 4 layers, single
Layer rate is 20%, and using atomic force microscope to record average-size is 13 μm, uses p owder resistivity instrument to record powder resistivity and is
90μΩ·m.Ash is 0.05wt%, and using atomic absorption spectrum to record metal ion content is 10ppm.
Embodiment 2
(1) blocky graphite that 10g particle diameter is 5 μm is joined in the aqueous solution that 2000mL contains 3g sodium bicarbonate, 70
DEG C stirring 2h；
(2) add 5g sulphuric acid, use 150 watts of power, ultrasonic 10 minutes.
(3) it is washed with deionized to neutrality, bottom centrifugal segregation, after insoluble matter, obtains graphene dispersing solution；
(4) gained graphene dispersing solution is dried, obtains graphene powder.
Graphene productivity is 90%, and using physical adsorption appearance to record specific surface area is 584m2/ g, the average number of plies is 4.5 layers,
Monolayer rate is 18%, and using atomic force microscope to record average-size is 3 μm, uses p owder resistivity instrument to record powder resistivity and is
100μΩ·m.Ash is 0.06wt%, and using atomic absorption spectrum to record metal ion content is 35ppm.
Embodiment 3
(1) amorphous graphite that 10g particle diameter is 1 μm is joined in the ethanol solution that 3000mL contains 2g potassium carbonate, 100
DEG C stirring 3h；
(2) add 5g formic acid, use 200 watts of power, ultrasonic 8 minutes.
(3) with absolute ethanol washing to neutral, graphene dispersing solution bottom centrifugal segregation, after insoluble matter, is obtained；
(4) gained graphene dispersing solution is dried, obtains graphene powder.
Graphene productivity is 90%, and using physical adsorption appearance to record specific surface area is 1310m2/ g, the average number of plies is 2 layers,
Monolayer rate is 45%, and using atomic force microscope to record average-size is 500nm, uses p owder resistivity instrument to record powder resistivity
It is 60 μ Ω m.Ash is 0.07wt%, and using atomic absorption spectrum to record metal ion content is 40ppm.
Embodiment 4
(1) amorphous graphite that 10g particle diameter is 30 μm is joined 4000mL and contain 1g sodium bicarbonate and the third of 1g potassium carbonate
In ketone solution, stir 2h at 120 DEG C；
(2) add 3g sulphuric acid and 3g acetic acid, use 50 watts of power, ultrasonic 3 minutes.
(3) with washing with acetone to neutral, graphene dispersing solution bottom centrifugal segregation, after insoluble matter, is obtained；
(4) gained graphene dispersing solution is dried, obtains graphene powder.
Graphene productivity is 80%, and using physical adsorption appearance to record specific surface area is 420m2/ g, the average number of plies is 6 layers, single
Layer rate is 10%, and using atomic force microscope to record average-size is 15 μm, uses p owder resistivity instrument to record powder resistivity and is
85μΩ·m.Ash is 0.09wt%, and using atomic absorption spectrum to record metal ion content is 44ppm.
Embodiment 5
(1) crystalline flake graphite that 10g particle diameter is 40 μm is joined 5000mL and contain 1g potassium carbonate and the ethanol of 1g sodium carbonate
In aqueous solution (mass fraction 40wt%), stir 3h at 120 DEG C；
(2) add 4g phosphoric acid and 2g nitric acid, use 10 watts of power, ultrasonic 1 minute.
(3) with the washing of 40wt% ethanol water to neutral, graphene dispersing solution bottom centrifugal segregation, after insoluble matter, is obtained；
(4) gained graphene dispersing solution is dried, obtains graphene powder.
Graphene productivity is 70%, and using physical adsorption appearance to record specific surface area is 300m2/ g, the average number of plies is 9 layers, single
Layer rate is 6%, and using atomic force microscope to record average-size is 23 μm, and using p owder resistivity instrument to record powder resistivity is 93
μΩ·m.Ash is 0.09wt%, uses atomic absorption spectrum to record metal ion content less than 45ppm.
Claims (9)
1. the method for a quick preparation high-quality Graphene, it is characterised in that comprise the following steps:
(1) graphite powder is joined in the solution containing intercalator it is stirred；
(2) add stripping auxiliary agent, carry out supersound process simultaneously；
(3) the solvent washing used with step (1) solution is the most neutral, obtains graphene dispersion bottom centrifugal segregation after insoluble matter
Liquid；
(4) gained graphene dispersing solution is dried, obtains Graphene.
The method of a kind of quick preparation high-quality Graphene the most as claimed in claim 1, it is characterised in that described graphite powder
Including crystalline flake graphite, blocky graphite or amorphous graphite, particle diameter is 1-40 μm.
The method of a kind of quick preparation high-quality Graphene the most as claimed in claim 1, it is characterised in that described intercalator
For one or more in sodium bicarbonate, sodium carbonate, potassium carbonate.
The method of a kind of quick preparation high-quality Graphene the most as claimed in claim 1, it is characterised in that described containing is inserted
Solvent in the solution of layer agent is one or more in deionized water, ethanol, acetone.
The method of a kind of quick preparation high-quality Graphene the most as claimed in claim 1, it is characterised in that described stripping helps
Agent is one or more in sulphuric acid, hydrochloric acid, phosphoric acid, nitric acid, formic acid, acetic acid.
The method of a kind of quick preparation high-quality Graphene the most as claimed in claim 1, it is characterised in that described graphite powder,
Intercalator and the mass ratio peeling off auxiliary agent are 1:0.1-0.3:0.2-0.6, and graphite powder with the relative scale containing intercalant solution is
1g:100-500mL.
The method of a kind of quick preparation high-quality Graphene the most as claimed in claim 1, it is characterised in that described stirring is
Carrying out at 50-120 DEG C, mixing time is 1-3 h.
The method of a kind of quick preparation high-quality Graphene the most as claimed in claim 1, it is characterised in that described is ultrasonic
Power is 10-200 watt, and ultrasonic time is 1-15 minute.
9. the Graphene that prepared by the method as described in any one of claim 1-9, it is characterised in that Graphene specific surface area is
300-1310 m2/ g, the average number of plies is 2-9 layer, and monolayer rate is 6-45%, and average-size is 500nm-23 μm, and powder resistivity is
60-100μΩ·m。
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| CN201610150020.6A CN105836734A (en) | 2016-03-16 | 2016-03-16 | Rapid preparation method for high-quality graphene |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106896031A (en) * | 2017-02-22 | 2017-06-27 | 济宁利特纳米技术有限责任公司 | A kind of graphene oxide dispersion ash content detection method |
| CN109534330A (en) * | 2017-09-22 | 2019-03-29 | 天津大学 | A kind of large area lacks layer graphene and preparation method thereof |
| CN111157445A (en) * | 2019-12-27 | 2020-05-15 | 江苏天鹏电源有限公司 | Method for testing internal binding force of lithium ion battery material |
| CN113387349A (en) * | 2021-05-12 | 2021-09-14 | 无锡启仁化工科技有限公司 | Method for efficiently preparing graphene sol |
| CN114436250A (en) * | 2020-11-04 | 2022-05-06 | 四会富仕电子科技股份有限公司 | Method for preparing graphene through liquid-phase stripping |
| CN114477154A (en) * | 2022-03-19 | 2022-05-13 | 深圳材启新材料有限公司 | Preparation method of high-quality graphene |
| CN114735687A (en) * | 2022-05-11 | 2022-07-12 | 深圳材启新材料有限公司 | Synthetic method of graphene |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103382026A (en) * | 2012-05-02 | 2013-11-06 | 中国科学院上海硅酸盐研究所 | Low-cost mass preparation method of high-quality graphene |
| CN103570012A (en) * | 2013-10-29 | 2014-02-12 | 复旦大学 | Preparation method of graphene |
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2016
- 2016-03-16 CN CN201610150020.6A patent/CN105836734A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103382026A (en) * | 2012-05-02 | 2013-11-06 | 中国科学院上海硅酸盐研究所 | Low-cost mass preparation method of high-quality graphene |
| CN103570012A (en) * | 2013-10-29 | 2014-02-12 | 复旦大学 | Preparation method of graphene |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106896031A (en) * | 2017-02-22 | 2017-06-27 | 济宁利特纳米技术有限责任公司 | A kind of graphene oxide dispersion ash content detection method |
| CN109534330A (en) * | 2017-09-22 | 2019-03-29 | 天津大学 | A kind of large area lacks layer graphene and preparation method thereof |
| CN111157445A (en) * | 2019-12-27 | 2020-05-15 | 江苏天鹏电源有限公司 | Method for testing internal binding force of lithium ion battery material |
| CN111157445B (en) * | 2019-12-27 | 2022-12-27 | 江苏天鹏电源有限公司 | Method for testing internal binding force of lithium ion battery material |
| CN114436250A (en) * | 2020-11-04 | 2022-05-06 | 四会富仕电子科技股份有限公司 | Method for preparing graphene through liquid-phase stripping |
| CN113387349A (en) * | 2021-05-12 | 2021-09-14 | 无锡启仁化工科技有限公司 | Method for efficiently preparing graphene sol |
| CN114477154A (en) * | 2022-03-19 | 2022-05-13 | 深圳材启新材料有限公司 | Preparation method of high-quality graphene |
| CN114735687A (en) * | 2022-05-11 | 2022-07-12 | 深圳材启新材料有限公司 | Synthetic method of graphene |
| CN114735687B (en) * | 2022-05-11 | 2023-09-26 | 深圳材启新材料有限公司 | Synthesis method of graphene |
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