CN108190875A - A kind of method for preparing high quality big size graphene - Google Patents
A kind of method for preparing high quality big size graphene Download PDFInfo
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- CN108190875A CN108190875A CN201810213217.9A CN201810213217A CN108190875A CN 108190875 A CN108190875 A CN 108190875A CN 201810213217 A CN201810213217 A CN 201810213217A CN 108190875 A CN108190875 A CN 108190875A
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- graphene
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- ultrasonic disperse
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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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- 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
- C01B2204/32—Size or surface area
Abstract
A kind of method for preparing high quality big size graphene, includes the following steps：1) it is 1 in mass ratio by original graphite and KOH：5 15 ratio mixing grinding；2) powder after grinding is placed in tube furnace, keeps the temperature 60 minutes after being warming up to 800 DEG C, be cooled to room temperature, obtain KOH etching graphite；3) H per 5ml a concentration of 30%2O21g etching graphite and 4 10min of ultrasonic disperse are added in solution, then 30 120s of microwave irradiation, obtain graphene aggregation；4) ultrasonic disperse in the alcohol for being 99% in purity by obtained graphene aggregation, is then dried, and high-quality graphene is made.The present invention is easy to operate, at low cost, and without using strong oxidizer and strong acid, can greatly reduce pollution and destruction to environment and equipment；Obtained graphene flat appearance, full-size can reach 150 μm2, highest conductivity is up to 2 × 105S/m。
Description
Technical field
The invention belongs to new material technology field, more particularly to a kind of preparation method of graphene.
Background technology
Graphene is the cellular film that carbon atom is formed with sp2 hybrid forms, is a kind of two-dimentional material of graphene layers
Material.But before graphene is found, most of physicists at that time think：Thermodynamics fluctuation does not allow any two dimensional crystal
Exist under finite temperature, until single-layer graphene is prepared out in laboratory.Grapheme material is macroscopically showing page
" lamination shape " as rock；On microcosmic, structure cell atom is in three dimensions inner plane arrangement layered, layer with covalently bonded between atom
It closes, and atom between the layers is then interacted with Van der Waals force, therefore interatomic bonding action is far longer than in layer
The interaction of atom between layers, so as to make its compound (fullerene of 0 dimension, carbon nanometer of 1 dimension compared with other dimensions
The graphite of pipe, 3 dimensions) there are unique crystal structure and special light, electricity, sound, mechanical property, due to above-mentioned characteristic, graphene
Application prospect is very wide, from single-electronic transistor, bipolarity transistor, flexible transistor, li-ion electrode materials, super capacitor electricity
Pole material, solar cell window electrode to transmission line of electricity and space elevator have application, and in the near future, graphene will
Commercialized application can be obtained in various fields such as catalysis, electronics, the energy.And scientist has found that graphene has abnormal quantum
The special physical effect and performance such as Hall effect are generally considered the final substituted for silicon of meeting, so as to cause electronics industry again
Revolution.
Since the two scientist An Deliegaimu (Andre Geim) and Ke Siteya of Univ Manchester UK
Nuo Wo disappears few layer graphene that love (Konstantin Novoselov) is obtained with a kind of very simple mechanical separation method
And after obtaining the Nobel Prize in physics of 2010, the various methods for preparing graphene emerge in an endless stream, general next
It says, the method for preparing graphene has：Mechanical stripping method, oxidation-reduction method, liquid phase stripping method, electrochemical process etc., in the above method
The method of middle micromechanics stripping is to remove graphite repeatedly using photoresist by mechanical means to obtain the method for graphene, this method
Simply, it is but time-consuming and laborious, poor repeatability, it is difficult to accurate control；Current most common method is oxide-reduction method, substantially former
Reason is to handle graphite by strong strong protonic acid, forms compound between graphite layers, is then aoxidized with strong oxidizer, forms graphite oxide
Alkene, then add in reducing agent redox graphene in reduction step and obtain graphene, but this method is in the mistake for preparing graphene
Strong oxidizer and strong acid have been used in journey, has there is very big damage to equipment, and the reducing agent used in reduction step is toxic,
Very big harm can be all generated to operating personnel and environment, the graphene fold of gained compares multimass than relatively low；It is also a kind of
Common method is liquid phase stripping method, and this method is made to shell graphite under the auxiliary of ultrasonic means using surfactant
From, but this method ultrasound needs super some time, productivity ratio relatively low.Cleaning of the later stage for the surfactant on graphene
And the comparatively laborious and a large amount of water of needs, it is undoubtedly for the deficienter overall situation of water resource instantly and makes the matter worse.
In addition the size of the graphene of liquid phase stripping gained is also smaller (general≤5 μm).
Therefore the non-acid preparation of graphene is a kind of urgent green technology yet-to-be developed, also becomes research graphite both at home and abroad
A big hot spot prepared by alkene.
Invention content
The purpose of the invention is to be directed to it is above-mentioned technically deficiency, provide and a kind of prepare high quality large scale stone
The method of black alkene.
The present invention is as follows：
(1) it is 1 by the ratio of the quality of original graphite and KOH：The ratio of 5-15 grinds original graphite and the abundant mixings of KOH
Mill；The original graphite is the natural flake graphite of 50-500 mesh；
(2) powder that step (1) is ground is put into crucible and is placed in tube furnace, with the heating rate of 15 DEG C/min,
60 minutes are kept the temperature after 800 DEG C are warming up in ar gas environment, is subsequently cooled to room temperature, obtains KOH etching graphite；
(3) H per 5mL a concentration of 30%2O2The etching graphite 1g and ultrasonic disperse 4- obtained by step (2) are added in solution
10min, then the etching graphite complete to ultrasonic disperse carry out microwave irradiation 30-120s, the power of microwave irradiation is 500w, is obtained
Graphene aggregation；
(4) step (3) is obtained into graphene aggregation ultrasonic disperse in alcohol of the purity for 99%, then dries, make
Can be reached by obtaining full-size by 150 μm2, conductivity reaches as high as 2 × 105The high quality big size graphene of S/m.
Compared with the prior art, the present invention has the following advantages：
1st, directly original graphite is etched with KOH, uses H again later2O2Intercalation stripping is carried out, it is easy to operate, time saving
It is laborsaving, cost-effective.
2nd, compared to conventional method, the present invention is without using strong oxidizer and strong acid, so as to greatly reduce to environment and set
Standby pollution and destruction；Also without using reducing agent, so as to avoid injury of the toxic reducing agent to operating personnel.
3rd, obtained graphene flat appearance, full-size can reach 150 μm2；Highest conductivity is up to 2 × 105S/m,
For one of peak of obtained graphene conductive rate so far；The graphene prepared is in ultracapacitor, lithium ion battery, conduction
Packing material etc. has application value.
Description of the drawings
Fig. 1 is graphene scanning electron microscope (SEM) photograph prepared by the embodiment of the present invention 1.
Fig. 2 is graphene transmission electron microscope picture prepared by the embodiment of the present invention 1.
Specific embodiment
Embodiment 1
By the original graphite of 50 mesh of 1g and the abundant mixing grindings of 10gKOH；Powder after grinding is put into juxtaposition in crucible
In in tube furnace, 60 minutes are kept the temperature after 800 DEG C are warming up in ar gas environment with the heating rate of 15 DEG C/min, is then cooled down again
To room temperature, KOH etching graphite is obtained；The H that 5mL a concentration of 30% is added in graphite is etched to 1g2O2Solution and ultrasonic disperse 5min
And then microwave irradiation 90s is carried out to the complete etching graphite of ultrasonic disperse, the power of microwave irradiation is 500w, obtains graphene
Aggregation；Ultrasonic disperse in the alcohol for being 99% in purity by obtained graphene aggregation, is then dried, and it is 150 μ that size, which is made,
m2, conductivity be up to 2 × 105The high-quality graphene of S/m.
As shown in Figure 1, by the high-degree of conversion by graphite to graphene, the full-size of gained graphene can reach 150 μ
m2It is and more transparent.
As shown in Fig. 2, further illustrate that the graphene of gained is more transparent, than relatively thin.
Embodiment 2
By the original graphite of 1g100 mesh original graphites and the abundant mixing grindings of 5gKOH；Powder after grinding is put into crucible
In be placed in tube furnace, keep the temperature 60 minutes after 800 DEG C are warming up in ar gas environment with the heating rate of 15 DEG C/min, then
Room temperature is cooled to, obtains KOH etching graphite；The H that 5mL a concentration of 30% is added in graphite is etched to 1g2O2Solution and ultrasound point
It dissipates 4min and then microwave irradiation 60s is carried out to the complete etching graphite of ultrasonic disperse, the power of microwave irradiation is 500w, is obtained
Graphene aggregation；Ultrasonic disperse in the alcohol for being 99% in purity by obtained graphene aggregation, is then dried, and size is made
It is 120 μm2, conductivity be up to 1.9 × 105The high-quality graphene of S/m.
Embodiment 3
By the original graphite of 1g300 mesh and the abundant mixing grindings of 7gKOH；Powder after grinding is put into crucible and is placed in
In tube furnace, 60 minutes are kept the temperature after 800 DEG C are warming up in ar gas environment with the heating rate of 15 DEG C/min, is then cooled to
Room temperature obtains KOH etching graphite；The H that 5mL a concentration of 30% is added in graphite is etched to 1g2O2Solution and ultrasonic disperse 8min it
Afterwards, then to the complete etching graphite of ultrasonic disperse microwave irradiation 30s is carried out, the power of microwave irradiation is 500w, obtains graphene and gathers
Collective；Ultrasonic disperse in the alcohol for being 99% in purity by obtained graphene aggregation, is then dried, and it is 90 μm that size, which is made,2、
Conductivity is up to 1.8 × 105The high-quality graphene of S/m.
Embodiment 4
By the original graphite of 1g50 mesh and the abundant mixing grindings of 12gKOH；Powder after grinding is put into crucible and is placed in
In tube furnace, 60 minutes are kept the temperature after 800 DEG C are warming up in ar gas environment with the heating rate of 15 DEG C/min, is then cooled to
Room temperature obtains KOH etching graphite；The H that 5mL a concentration of 30% is added in graphite is etched to 1g2O2Solution and ultrasonic disperse 10min
And then microwave irradiation 120s is carried out to the complete etching graphite of ultrasonic disperse, the power of microwave irradiation is 500w, obtains graphene
Aggregation；Ultrasonic disperse in the alcohol for being 99% in purity by obtained graphene aggregation, is then dried, and it is 130 μ that size, which is made,
m2, conductivity be up to 2 × 105The high-quality graphene of S/m.
Embodiment 5
By the abundant mixing grindings of the KOH of the original graphite of 1g500 mesh and 15g；Powder after grinding is put into crucible simultaneously
It is placed in tube furnace, 60 minutes is kept the temperature after 800 DEG C are warming up in ar gas environment with the heating rate of 15 DEG C/min, it is then cold again
But to room temperature, KOH etching graphite is obtained；The H that 5mL a concentration of 30% is added in graphite is etched to 1g2O2Solution and ultrasonic disperse
The 6min and then etching graphite progress microwave irradiation 90s complete to ultrasonic disperse, the power of microwave irradiation is 500w, obtains stone
Black alkene aggregation；Ultrasonic disperse in the alcohol for being 99% in purity by obtained graphene aggregation, is then dried, obtained size is
80μm2, conductivity be up to 1.8 × 105The high-quality graphene of S/m.
Claims (4)
- A kind of 1. method for preparing high quality big size graphene, it is characterised in that：It includes the following steps：(1) it is 1 by the mass ratio of original graphite and KOH：The ratio of 5-15 grinds original graphite and the abundant mixings of KOH；(2) powder after step (1) is ground, which is put into crucible, to be placed in tube furnace, and 800 DEG C are warming up in ar gas environment 60 minutes are kept the temperature afterwards, is subsequently cooled to room temperature, obtains KOH etching graphite；(3) H per 5ml a concentration of 30%2O2The etching graphite 1g and ultrasonic disperse 4- obtained by step (2) are added in solution 10min, then the etching graphite complete to ultrasonic disperse progress microwave irradiation 30-120s, obtains graphene aggregation；(4) step (3) is obtained into graphene aggregation ultrasonic disperse in alcohol of the purity for 99%, then dries, finally make Can be reached by obtaining full-size by 150 μm2High-quality graphene.
- 2. the method according to claim 1 for preparing high quality big size graphene, it is characterised in that：The original graphite Natural flake graphite for 50-500 mesh.
- 3. the method according to claim 1 for preparing high quality big size graphene, it is characterised in that：Liter in tube furnace Warm rate is 15 DEG C/min.
- 4. the method according to claim 1 for preparing high quality big size graphene, it is characterised in that：The microwave shines The power penetrated is 500w.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108557813A (en) * | 2018-07-26 | 2018-09-21 | 杭州高烯科技有限公司 | The method that one-step method prepares oversize single-layer graphene oxide |
| CN110550623A (en) * | 2019-10-16 | 2019-12-10 | 燕山大学 | Method for preparing high-quality large-size graphene on large scale |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101696002A (en) * | 2009-10-14 | 2010-04-21 | 苏州纳米技术与纳米仿生研究所 | Graphene and semiconductor nano particle compound system and synthesizing method thereof |
| CN104058396A (en) * | 2014-07-14 | 2014-09-24 | 复旦大学 | Method for preparing large-size high-quality graphene with controllable number of layers |
| CN105800603A (en) * | 2016-04-22 | 2016-07-27 | 华侨大学 | Method for quickly preparing high-quality graphene |
-
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- 2018-03-15 CN CN201810213217.9A patent/CN108190875A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101696002A (en) * | 2009-10-14 | 2010-04-21 | 苏州纳米技术与纳米仿生研究所 | Graphene and semiconductor nano particle compound system and synthesizing method thereof |
| CN104058396A (en) * | 2014-07-14 | 2014-09-24 | 复旦大学 | Method for preparing large-size high-quality graphene with controllable number of layers |
| CN105800603A (en) * | 2016-04-22 | 2016-07-27 | 华侨大学 | Method for quickly preparing high-quality graphene |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108557813A (en) * | 2018-07-26 | 2018-09-21 | 杭州高烯科技有限公司 | The method that one-step method prepares oversize single-layer graphene oxide |
| CN110550623A (en) * | 2019-10-16 | 2019-12-10 | 燕山大学 | Method for preparing high-quality large-size graphene on large scale |
| CN110550623B (en) * | 2019-10-16 | 2022-07-29 | 燕山大学 | Method for preparing high-quality large-size graphene on large scale |
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