CN110203913A - A method of preparing graphene - Google Patents
A method of preparing graphene Download PDFInfo
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- CN110203913A CN110203913A CN201910460949.2A CN201910460949A CN110203913A CN 110203913 A CN110203913 A CN 110203913A CN 201910460949 A CN201910460949 A CN 201910460949A CN 110203913 A CN110203913 A CN 110203913A
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- graphene
- preparing graphene
- hydrogen peroxide
- expanded graphite
- graphite
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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
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
Abstract
The invention discloses a kind of methods for preparing graphene.This graphene is made by preparation method below: 1) expansible graphite being carried out expansion process, then crushed, obtain expanded graphite powder；2) expanded graphite powder and hydrogen peroxide are mixed, then deaerated, then carried out ultrasonic removing, reheat and decompose hydrogen peroxide, then dry, obtain graphene.The present invention provides a kind of method for being suitable for large-scale production and preparation graphene, this method green non-pollution, safety and environmental protections.The graphene being prepared by the method for the invention has many advantages, such as of uniform size, and defect is few.
Description
Technical field
The invention belongs to technical field of graphene, and in particular to a method of prepare graphene.
Background technique
Graphene is a kind of carbon atom single layer for forming hexangle type in honeycomb lattice by sp2 hybridized orbit.Graphene is structure
The basic unit for building other dimension carbon materials, when it existing way change when, can be respectively formed fullerene, carbon nanotube and
Graphite etc..Graphene has the performances such as excellent electricity, optics, mechanics, and in addition there are excellent heating conductions and high
Charge carrier mobility, due to these excellent properties, so that it is in such as composite material, the energy, big health, sea water desalination
Etc. various fields become the hot spot of research.Various fields have also derived and many have prepared graphene to the difference of graphene demand
Method and technique.
The common method for preparing graphene mainly includes mechanical stripping method, and vapour deposition process, epitaxial growth method and oxidation are also
Former method, mechanical stripping method are only suitable for laboratory preparation graphene sample, and vapour deposition process and epitaxial growth method want technology to equipment
It is more demanding, production difficulty is larger, although oxidation-reduction method can with mass production, prepare product defects it is more, and produce
It is seriously polluted in the process.Subsequent also someone develops wet grinding technique and prepares graphene, i.e., using crystalline flake graphite as raw material, by it
Dispersion in a solvent, using mechanical force removes graphite at graphene.Although whole preparation process is environmentally protective, and obtained stone
The quality of black alkene product is relatively also higher, and the Van der Waals force of graphite layers is larger, to be prepared into the time that graphene needs to remove
Relatively long, therefore the graphene of wet process removing preparation is caused to hold at high price.
Expansible graphite is that a kind of method using physically or chemically makes non-carbon qualitative response object be inserted into graphite layers, with charcoal
The hexagonal network planar junction of element maintains the crystalline compounds of graphite laminate structure again while conjunction.When expansible graphite encounters height
Wen Shi, intercalation compound will decompose, and generate a kind of thrust along graphite layers C axis direction, this thrust is much larger than graphite ion
Inter-layer bonding force, can graphite layers be open, form vermiform expanded graphite.For crystalline flake graphite,
The interlamellar spacing of expanded graphite is bigger, and Van der Waals force between layers is smaller, it is easier to which removing is prepared into graphene.
In existing disclosed document, for CN107500279A using expansible graphite as raw material, graphene quantum dot is stripper,
Using mechanical stripping method and it is furnished with twice ultrasonic treatment process, to realize that mass production prepares graphene.But graphene amount
The price of son point is much higher than the price of graphene, although partially recycled can also recycle, the graphene of removing is micro-nano
Rank.Graphene quantum dot is well dispersed in the graphene system after removing, and recovery utilization rate is extremely low.Although this method can
With the simple and quick graphene product that obtains, but it is high to be limited to preparation cost, can not large-scale production.
After CN103950927A mixes expanded graphite and sodium bicarbonate solution, 1.5h is stirred under the conditions of being warming up to 190 DEG C
Afterwards, generation carbon dioxide is decomposed using sodium bicarbonate generate peeling force, and carbon dioxide solubility in expansible graphite piece interlayer
After in water, the alkaline condition of formation makes graphene film interlayer form electrostatic repulsion, to form graphene.But preparation process
In need high temperature and pressure, energy consumption is high, and the sodium bicarbonate introduced is more difficult by except clean.
In addition, there are many more the research report of graphene is prepared about expanded graphite, but more or less have the following problems:
After expansible graphite expanding treatment, unexpanded raw material separation problem；The removing mode problem of expanded graphite stripping bench；Removing
Charge stripping efficiency, cost and the later period of the up-stripping auxiliary agent of Shi Xuanyong remove the difficulty or ease problem etc. of up-stripping auxiliary agent.
Summary of the invention
In order to overcome the above problem of the existing technology, environmentally protective stone is prepared the purpose of the present invention is to provide a kind of
The method of black alkene.
In order to achieve the above purpose, the technical solution used in the present invention is:
The present invention provides a kind of method for preparing graphene, this preparation method the following steps are included:
1) expansible graphite is subjected to expansion process, then crushed, obtain expanded graphite powder；
2) expanded graphite powder and hydrogen peroxide are mixed, then deaerated, then carry out ultrasonic removing, reheating is decomposed double
Oxygen water, is then dried, and obtains graphene.
Preferably, this method and step 1 for preparing graphene) in, the partial size of expansible graphite is 50 mesh~100 mesh.
Preferably, this method and step 1 for preparing graphene) in, the expansion multiplying power of expansible graphite is 200~400 times；
It is further preferred that the expansion multiplying power of expansible graphite is 250~350 times.
Preferably, this method and step 1 for preparing graphene) in, carbon content >=98wt% of expansible graphite.
Preferably, this method and step 1 for preparing graphene) in, expansion process is thermal expansion processing, microwave expansion processing
One or both of.
Preferably, this method and step 1 for preparing graphene) expansion process in, thermal expansion processing refers to will be inflatable
Graphite, which is placed in nitrogen or inert gas atmosphere, heats expansion process, and the temperature of heating is 600 DEG C~800 DEG C, expansion process
Time be 30s~90s；It is heated to it is further preferred that thermal expansion processing refers to for expansible graphite to be placed in nitrogen atmosphere
650 DEG C~750 DEG C expansion process 50s~70s.
Preferably, this method and step 1 for preparing graphene) in, crush as one of ball milling, grinding, airflow milling or
It is a variety of.
Preferably, this method and step 1 for preparing graphene) in, the partial size D50 of material is crushed to no more than 20 μm；Into
One step is preferred, is crushed to the partial size D50 of material no more than 10 μm.
Preferably, this method and step 2 for preparing graphene) in, the mass ratio of expanded graphite powder and hydrogen peroxide is 1:
(10~100).
Preferably, this method and step 2 for preparing graphene) in, the H of hydrogen peroxide2O2Mass percent is 5%~50%；
It is further preferred that the H of hydrogen peroxide2O2Mass percent is 10%~40%.
Preferably, this method and step 2 for preparing graphene) in, the time of mixing is 3min~10min；Into one
Step is preferred, and the time of mixing is 4min~6min.
Preferably, this method and step 2 for preparing graphene) in, the mode of degassing is vacuum outgas.
Preferably, this method and step 2 for preparing graphene) in, degassing is specially the vacuum outgas at 1~10kPa
3min~10min.
Preferably, this method and step 2 for preparing graphene) in, the temperature of ultrasound removing is 50 DEG C~100 DEG C；Into one
Step is preferred, and the temperature of ultrasound removing is 50 DEG C~80 DEG C；Still further preferably, the temperature of ultrasound removing is 50 DEG C~60
℃。
Preferably, this method and step 2 for preparing graphene) in, the time of ultrasound removing is 0.5h~2h；It is further excellent
Choosing, the time of ultrasound removing is 1h~2h.
Preferably, this method and step 2 for preparing graphene) in, ultrasonic power is 0.5kW~3kW, ultrasonic frequency
For 20kHz~60kHz.
Preferably, this method and step 2 for preparing graphene) in, the temperature of heat resolve is 100 DEG C~160 DEG C.
Preferably, this method and step 2 for preparing graphene) in, the time of heat resolve is 0.5h~2h；It is further excellent
Choosing, the time of heat resolve is 1h~2h.
This method and step 2 for preparing graphene) in, it is water by heating heat resolve hydrogen peroxide after ultrasound removing
And oxygen；It, can be by carrying out titration test with liquor potassic permanganate during heating up heating, whether detection hydrogen peroxide divides
Solution is complete.
Preferably, this method and step 2 for preparing graphene) in, dry mode is spray drying.
It the present invention also provides a kind of graphene, is made by above-mentioned method.
The beneficial effects of the present invention are:
The present invention provides a kind of method for being suitable for large-scale production and preparation graphene, this method green non-pollution, peaces
Loopful is protected.The graphene being prepared by the method for the invention has many advantages, such as of uniform size, and defect is few.
Compared with prior art, advantages of the present invention is specific as follows:
1, the present invention is using expansible graphite as raw material, after expanding treatment, the layer of the interlamellar spacing of product than crystalline flake graphite
Spacing is big, and Van der Waals force is smaller, and the energy that when removing needs is less.It is shelled than tradition using crystalline flake graphite or highly oriented pyrolytic graphite
From when time it is shorter, charge stripping efficiency is higher.And using graphite oxide is raw material, and preparation process is complicated, and it is with high costs, until
It is less 5 times or more of expansible graphite.
2, pulverization process is carried out to the sample before ultrasound removing, sample is smaller, and ultrasound acts on " empty on sample when removing
Cave effect " is more obvious, so that sample is easier to be stripped.
3, using hydrogen peroxide as stripping solution, the surface tension of hydrogen peroxide is smaller for deionized water, it is easier to moisten
Hygral expansion graphite.Also be de-gassed so that hydrogen peroxide be easier to replace between the gap for penetrating into expanded graphite it is original
Air, so that the abundant swells graphite of hydrogen peroxide.Ultrasonic stripping bench, hydrogen peroxide slowly decomposes when heating, generation
Expanded graphite is completely exfoliated out bubble, and when ultrasound removing, " void effect " collaboration hydrogen peroxide generated using ultrasound is generated
Bubble graphene is completely exfoliated into expanded graphite.After the completion of to be stripped, after heating decomposes hydrogen peroxide completely, by graphene
Product can be obtained in drying.Entire charge stripping efficiency is efficiently convenient, and in production process no three wastes discharge, charge stripping efficiency outclass
The efficiency removed using water or organic solvent.And splitting time is short, the defect of obtained product is small, partial size more evenly, quality
More preferably.
4, in entire production process, low energy consumption, and safety, efficiently, and production process is environmentally protective, is easy to amplify and promote.
Detailed description of the invention
Fig. 1 is Sample Scan electron microscope made from embodiment 1；
Fig. 2 is Sample Scan electron microscope made from comparative example 1.
Specific embodiment
The contents of the present invention are described in further detail below by way of specific embodiment.Original used in embodiment
Material unless otherwise specified, can be obtained from routine business approach.
Embodiment 1
The graphene preparation method of this example is as follows:
100g carbon content 99wt%, 80 mesh, 300 times of expansion multiplying power of expanded graphite are placed in high-temperature expansion furnace, in nitrogen
Atmosphere enclose in after 700 DEG C of expansion 60s, by the sample after expansion using airslide disintegrating mill grind partial size to D50 be 10 μm.Take 10g
After sample after grinding is placed in flask, 500mLH is added2O25min is continuously stirred after the hydrogen peroxide that mass percent is 30%,
After vacuum outgas 5min, 60 DEG C are warming up to, after the continuous removing 1h of the ultrasound of 3kW, 30kHz, it is straight to be warming up to 150 DEG C of stirring 1h
To after no blistering (judging that decomposing hydrogen dioxide solution is complete using liquor potassic permanganate titration), graphene sample is can be obtained in spray drying
Product.
Embodiment 2
The graphene preparation method of this example is as follows:
100g carbon content 99wt%, 100 mesh, 300 times of expansion multiplying power of expanded graphite are placed in high-temperature expansion furnace, in nitrogen
Atmosphere enclose in after 700 DEG C of expansion 60s, by the sample after expansion using airslide disintegrating mill grind partial size to D50 be 8 μm.10g is taken to grind
After sample after mill is placed in flask, 800mLH is added2O25min is continuously stirred after the hydrogen peroxide that mass percent is 20%, very
After sky degassing 5min, be warming up to 70 DEG C, after the continuous removing 1h of the ultrasound of 2kW, 30kHz, be warming up to 150 DEG C of stirring 1h up to
After no blistering (judging that decomposing hydrogen dioxide solution is complete using liquor potassic permanganate titration), graphene sample is can be obtained in spray drying.
Embodiment 3
The graphene preparation method of this example is as follows:
80g carbon content 99wt%, 50 mesh, 300 times of expansion multiplying power of expanded graphite are placed in high-temperature expansion furnace, in nitrogen
In atmosphere after 700 DEG C of expansion 60s, by the sample after expansion using airslide disintegrating mill grind partial size to D50 be 10 μm.10g is taken to grind
After sample after mill is placed in flask, 1000mLH is added2O25min is continuously stirred after the hydrogen peroxide that mass percent is 30%, very
After sky degassing 5min, 60 DEG C are warming up to, after the continuous removing 0.5h of the ultrasound of 1kW, 30kHz, it is straight to be warming up to 155 DEG C of stirring 2h
To after no blistering (judging that decomposing hydrogen dioxide solution is complete using liquor potassic permanganate titration), graphene sample is can be obtained in spray drying
Product.
Comparative example 1
This example sample the preparation method is as follows:
By 100g carbon content 99wt%, 80 mesh, 300 times of expansion multiplying power of expanded graphite are placed in high-temperature expansion furnace, in nitrogen
Atmosphere enclose in after 700 DEG C of expansion 60s, by the sample after expansion using airslide disintegrating mill grind partial size to D50 be 10 μm.Take 10g
After sample after grinding is placed in flask, 5min is continuously stirred after 500mL deionized water is added, after vacuum outgas 5min, heating
To 60 DEG C, after the continuous removing 1h of the ultrasound of 3kW, 30kHz, after being warming up to 150 DEG C of stirring 1h, spray drying be can be obtained
The mixing sample of graphene and expanded graphite.
Sample Scan electron microscope made from embodiment 1 is shown in attached drawing 1, and the Sample Scan electron microscope of comparative example 1 is shown in attached drawing 2.It is logical
Cross Fig. 1 and Fig. 2 SEM figure comparison it is found that sample particle diameter made from embodiment 1 more evenly, defect is few, it was demonstrated that peeling effect is more
It is good.And sample size removes further expansion with ultrasound in sample made from comparative example 1, but there are also unstripped swollen simultaneously
The presence of the structure of swollen graphite, peeling effect are poor.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of method for preparing graphene, it is characterised in that: the following steps are included:
1) expansible graphite is subjected to expansion process, then crushed, obtain expanded graphite powder；
2) expanded graphite powder and hydrogen peroxide are mixed, then deaerated, then carried out ultrasonic removing, reheat and decompose dioxygen
Then water is dried, graphene is obtained.
2. a kind of method for preparing graphene according to claim 1, it is characterised in that: in step 1), expansion process is
One or both of thermal expansion processing, microwave expansion processing.
3. a kind of method for preparing graphene according to claim 1, it is characterised in that: in step 1), crush for ball milling,
One of grinding, airflow milling are a variety of.
4. a kind of method for preparing graphene according to claim 3, it is characterised in that: in step 1), be crushed to material
Partial size D50 be not more than 20 μm.
5. a kind of method for preparing graphene according to claim 1, it is characterised in that: in step 2), expanded graphite powder
The mass ratio of material and hydrogen peroxide is 1:(10~100).
6. a kind of method for preparing graphene according to claim 5, it is characterised in that: in step 2), the H of hydrogen peroxide2O2
Mass percent is 5%~50%.
7. a kind of method for preparing graphene according to claim 1, it is characterised in that: in step 2), the mode of degassing
For vacuum outgas.
8. a kind of method for preparing graphene according to claim 1, it is characterised in that: in step 2), ultrasound removing
Temperature is 50 DEG C~100 DEG C, and the time of ultrasound removing is 0.5h~2h.
9. a kind of method for preparing graphene according to claim 1, it is characterised in that: in step 2), heat resolve
Temperature is 100 DEG C~160 DEG C, and the time of heat resolve is 0.5h~2h.
10. a kind of graphene, it is characterised in that: be made by method according to any one of claims 1 to 9.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110615430A (en) * | 2019-10-17 | 2019-12-27 | 桂林理工大学 | Novel preparation method of primary few-layer graphene |
| CN111285361A (en) * | 2020-04-14 | 2020-06-16 | 中北大学 | High-efficiency liquid-phase mechanical preparation method of low-defect and high-dispersion graphene |
| CN115231582A (en) * | 2022-07-19 | 2022-10-25 | 西安交通大学 | Two-dimensional montmorillonite large-size nanosheet stripping method |
| WO2023087135A1 (en) * | 2021-11-16 | 2023-05-25 | 广东聚石化学股份有限公司 | Method for preparing graphene |
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| CN109438748A (en) * | 2018-10-12 | 2019-03-08 | 苏州鼎烯聚材纳米科技有限公司 | A kind of continuous producing method of the high thermal conductivity graphene latex foam for mattress |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110615430A (en) * | 2019-10-17 | 2019-12-27 | 桂林理工大学 | Novel preparation method of primary few-layer graphene |
| CN111285361A (en) * | 2020-04-14 | 2020-06-16 | 中北大学 | High-efficiency liquid-phase mechanical preparation method of low-defect and high-dispersion graphene |
| CN111285361B (en) * | 2020-04-14 | 2022-12-27 | 中北大学 | High-performance liquid-phase mechanical preparation method of low-defect and high-dispersion graphene |
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| CN115231582A (en) * | 2022-07-19 | 2022-10-25 | 西安交通大学 | Two-dimensional montmorillonite large-size nanosheet stripping method |
| CN115231582B (en) * | 2022-07-19 | 2023-12-19 | 西安交通大学 | Two-dimensional montmorillonite large-scale-diameter nano sheet stripping method |
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