CN104505512B - Method for preparing microcrystalline graphene through ball milling - Google Patents
Method for preparing microcrystalline graphene through ball milling Download PDFInfo
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- CN104505512B CN104505512B CN201410690141.0A CN201410690141A CN104505512B CN 104505512 B CN104505512 B CN 104505512B CN 201410690141 A CN201410690141 A CN 201410690141A CN 104505512 B CN104505512 B CN 104505512B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a method for preparing microcrystalline graphene through ball milling, and belongs to the field of preparation of functional materials. The method comprises: firstly performing shock-heating and shock-cooling processing on microcrystalline graphene, then performing ball milling, and doping nitrogen in the ball milling process, so as to obtain the nitrogen-doped microcrystalline graphene material. The method is simple in technology, strong in operation controllability and stable in product quality. Microcrystalline graphene can be directly used as a raw material, which is wide in source and low in price and suitable for large-scale production. The prepared nitrogen-doped microcrystalline graphene possesses the characteristics of being fluffy, light in mass and large in specific surface area. Because of doping of nitrogen atom, active site is increased, the energy level of the carbon structure is changed, and the prepared microcrystalline graphene is suitable for preparing high-capacity good-rate-capability lithium ion cathode materials.
Description
Technical field
The invention belongs to functional material preparation field, be specifically related to a kind of method that ball milling prepares micro crystal graphite alkene.
Background technology
Micro crystal graphite, is commonly called as amorphous graphite, and containing the crystallization graphite of 15% to 45%, average-size is 0.01
To 0.1 micron.Micro crystal graphite reserves are huge, and 1/3rd of cheap only crystalline flake graphite, tool
There is the wide market space.But owing to technological development puts into not, the research to micro crystal graphite is extremely short of,
Prepared micro crystal graphite alkene by micro crystal graphite and then prepare other functional material, such as lithium ion battery negative material
Probability the most sufficiently paid attention to.
Material with carbon element low price, good stability, is the most frequently used negative material of current commercial Li-ion batteries.
But, its theoretical capacity only has 372mAh g-1, actual reversible capacity is all at 300～340mAh g-1,
Low battery capacity and limited high rate performance, hinder the extensive application of lithium ion battery to a great extent.
Development high reversible capacity, the lithium ion battery of excellent high rate performance and high cyclical stability is extremely urgent.
And the method preparing carbon based negative electrodes material reported at present generally involve some exacting terms and
Low productivity, such as: under conditions of high-temperature calcination and highly basic activation, prepare the carbon fiber of N doping, stratiform hydrogen
Between oxide, the nanometer carbon of 800 DEG C of growths, obtains many with nano-calcium carbonate for template high-temperature calcination gelatin
Hole carbon, with imidazoles as carbon source, grows the carbon pipe of Bamboo-shaped, with SiO under the conditions of 850 DEG C2Nanosphere is mould
Plate, high-temperature calcination Ovum Gallus domesticus album obtains the porous carbon of porous N doping.These preparation process need to use in general
To poisonous chemical reagent, need multiple loaded down with trivial details step, consume considerable time, and the product obtained
Measure low, so that the overall high cost of negative material, it is difficult to accomplish scale production.
Summary of the invention
The best for existing carbon based negative electrodes material property, and preparation process is loaded down with trivial details, condition is harsh, relate to
Toxic reagent, and the material yield prepared is low, causes totle drilling cost too high, it is difficult to accomplish scale production
Problem, by cheap micro crystal graphite is processed modification, the present invention proposes a kind of ball milling and prepares micro-
The method of brilliant Graphene, the method technique is simply suitable for large-scale production, and prepared micro crystal graphite alkene can be used for
Prepare the negative material of lithium ion battery.
Described method comprises the steps:
Step one, by micro crystal graphite with the ramp of 10 DEG C/min to 800～1200 DEG C, be incubated 5～10
Minute；
Step 2: the micro crystal graphite after step one heat treated is transferred to equipped with in the clean container of liquid nitrogen,
Every 100g micro crystal graphite correspondence at least 50ml liquid nitrogen, stands and treats liquid nitrogen volatilization completely；
Step 3: be transferred to the micro crystal graphite obtained in step 2 to substitute in the ball grinder of gas, and with 20
Steel ball is joined in ball grinder by the ratio of individual steel ball correspondence 200g microlite powdered ink；
Step 4: the ball grinder of step 3 is encapsulated, after ball grinder evacuation, is filled with nitrogen atmosphere, as
This is repeated 3 times above；
Step 5: the ball grinder described in step 4 is fixed on comprehensive ball milling instrument, at the frequency of 30～50Hz
Ball milling 80～120 hours under rate, obtain the stratiform micro crystal graphite alkene that described thickness is 1～3nm.
Beneficial effect
(1) present invention uses a kind of method of simple possible to prepare micro crystal graphite alkene, and quickly heating is with rapid
Cold process can make micro crystal graphite be more easily peelable layered graphene film, and the method technique is simple, environment is friendly
Good.
(2) the raw material micro crystal graphite that the present invention utilizes can be directly obtained by micro crystal graphite ore deposit, wide material sources,
Cheap, it is available for industrialization and produces in enormous quantities.
(3) the N doping micro crystal graphite alkene of the small pieces that the method for the invention obtains is sheet, has volume
Feature fluffy, that light weight, specific surface area are big, due to the doping of nitrogen-atoms, the energy level of carbon structure there occurs
Change, be suitable for preparing capacity height, the ion cathode material lithium of good rate capability, it is also possible to be used as efficient
Energy conversion and storage material, make up the deficiency of application in energy and material of large stretch of Graphene.
(4) micro crystal graphite is rich in minerals, but the traditional utilization in micro crystal graphite ore deposit generally requires through high temperature, pure
The loaded down with trivial details steps such as change, the method for the invention needs not move through these processes, greatly reduces microlite
The use cost of ink, extends its range of application.Both protect environment, create again economic benefit.
(5) the method for the invention is owing to introducing doping nitrogen-atoms so that avtive spot increases, as lithium electricity
Pond negative material can have good recursive nature and the capacity beyond general material with carbon element.
Accompanying drawing explanation
Fig. 1 is the Raman spectrogram of micro crystal graphite alkene of the present invention in embodiment 1；
Fig. 2 is the scanning electron microscope diagram of micro crystal graphite alkene of the present invention in embodiment 1；
Fig. 3 is the transmission electron microscope figure of micro crystal graphite alkene of the present invention in embodiment 1；
Fig. 4 is to test micro crystal graphite alkene of the present invention in embodiment 6 under 0.1A/g electric current to do negative material
The Capacity Plan of battery；
Fig. 5 be in embodiment 6 under different electric currents (0.1A/g to 45A/g), test crystallite of the present invention
Graphene does the high rate performance figure of negative material battery.
Detailed description of the invention
The present invention proposes a kind of straightforward procedure preparing lithium ion battery negative material, and the raw material of described method comes
Source is quite varied, cheap and easy to get, and preparation process is simple, environmental friendliness, low cost, applicable large-scale production.
The micro crystal graphite alkene using the ion cathode material lithium N doping that described method prepares is sheet,
Have the advantages that volume is fluffy, light weight, specific surface area are big.Due to the doping of nitrogen-atoms, the energy of carbon structure
Level there occurs change so that micro crystal graphite alkene has potential application as energy and material, is suitable for preparation and holds
Amount is high, the ion cathode material lithium of good rate capability, substantially increases the added value of micro crystal graphite.
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings, but is not limited to this.
Embodiment 1
The first step, weigh the micro crystal graphite 200g that purity is 80%；
Second step, load weighted micro crystal graphite is transferred in the magnetic boat of cleaning (magnetic boat width: 2cm, long: 5cm),
With the heating rates of 10 DEG C/min, temperature is increased to 800 DEG C, and maintains 5 minutes；
3rd step, while hot micro crystal graphite is transferred in the Dewar flask of 100mL liquid nitrogen；
4th step, treat liquid nitrogen volatilization completely, the micro crystal graphite processed through high temperature and quenching is transferred to 250mL
Can substitute in the ball grinder of gas；
5th step, diameter is respectively the steel ball 2 of 2cm, the steel ball of 1.2cm 8, the steel of 0.6cm
12, pearl is placed in above ready ball grinder；
6th step, encapsulation ball grinder, after ball grinder evacuation, be filled with nitrogen atmosphere, then evacuation, fill
Enter nitrogen atmosphere, be so repeated 2 times；
7th step, the ball grinder that will be filled with nitrogen are fixed on comprehensive ball milling instrument, ball under the frequency of 30Hz
Mill 80h.
The product obtained is detected, at 1350cm in the Raman collection of illustrative plates of Fig. 1-1And 1590cm-1Place occurs
The characteristic peak of Graphene, by X-ray powder diffraction test figure it can be seen that the characteristic peak of micro crystal graphite
(26 °) there occurs skew, about 23 ° appearance, illustrates that, in mechanical milling process, micro crystal graphite becomes graphite
Alkene；Test knowable to (as shown in Figures 2 and 3) in conjunction with scanning electron microscope and transmission electron microscope,
The structure of micro crystal graphite alkene is laminar structured, and size shows in tens nanometers to hundreds of nanometer, atomic force
Micro mirror test show the thickness of lamella 1～3nm, the test of x-ray photoelectron power spectrum shows the nitrating of Graphene
Amount is 1.7%.
Embodiment 2
The first step, weigh the micro crystal graphite 180g that purity is 84%；
Second step, load weighted micro crystal graphite is transferred in the magnetic boat of cleaning (magnetic boat width: 2cm, long: 5cm),
With the heating rate of 10 DEG C/min, temperature is increased to 1200 DEG C, and maintains 10 minutes；
3rd step, while hot micro crystal graphite is transferred in the Dewar flask of 100mL liquid nitrogen；
4th step, treat liquid nitrogen volatilization completely, the micro crystal graphite processed through high temperature and quenching is transferred to substitute
In the ball grinder of gas；
5th step, diameter is respectively the steel ball 3 of 2cm, the steel ball of 1.2cm 6, the steel ball of 0.6cm
10 are placed in above ready ball grinder；
6th step, encapsulation ball grinder, after ball grinder evacuation, be filled with nitrogen atmosphere, then evacuation, be filled with
Nitrogen atmosphere, is so repeated 3 times；
7th step, the ball grinder that will be filled with nitrogen are fixed on comprehensive ball milling instrument, ball under the frequency of 50Hz
Mill 120h.
The product obtained is detected, at 1350cm in Raman collection of illustrative plates-1And 1590cm-1Place occurs in that graphite
The characteristic peak of alkene, by X-ray powder diffraction test figure it can be seen that the characteristic peak (26 °) of micro crystal graphite is sent out
Give birth to skew, about about 23 ° appearance, illustrated that, in mechanical milling process, micro crystal graphite becomes Graphene；Knot
Closing scanning electron microscope and transmission electron microscope test understands, the structure of micro crystal graphite alkene is sheet knot
Structure, size in tens nanometers to hundreds of nanometer, atomic force microscope test show the thickness of lamella 1～
3nm, the test of x-ray photoelectron power spectrum shows that the itrogen content of getter with nitrogen doped of Graphene is 1.6%.
Embodiment 3
The first step, weigh the micro crystal graphite 140g that purity is 80%；
Second step, load weighted micro crystal graphite is transferred in the magnetic boat of cleaning (magnetic boat width: 2cm, long: 5cm),
With the heating rate of 10 DEG C/min, temperature is increased to 900 DEG C, and maintains 7 minutes；
3rd step, while hot micro crystal graphite is transferred in the Dewar flask of 80mL liquid nitrogen；
4th step, treat liquid nitrogen volatilization completely, the micro crystal graphite processed through high temperature and quenching is transferred to 250mL
Can substitute in the ball grinder of gas；
5th step, diameter is respectively the steel ball 4 of 2cm, the steel ball of 1.2cm 10, the steel of 0.6cm
8, pearl is placed in above ready ball grinder；
6th step, encapsulation ball grinder, after ball grinder evacuation, be filled with nitrogen atmosphere, then evacuation, be filled with
Nitrogen atmosphere, is so repeated 2 times；
7th step, the ball grinder that will be filled with nitrogen are fixed on comprehensive ball milling instrument, ball under the frequency of 30Hz
Mill 120h.
The product obtained is detected, at 1350cm in Raman collection of illustrative plates-1And 1590cm-1Place occurs in that graphite
The characteristic peak of alkene, by X-ray powder diffraction test figure it can be seen that the characteristic peak (26 °) of micro crystal graphite is sent out
Give birth to skew, about about 23 ° appearance, illustrated that, in mechanical milling process, micro crystal graphite becomes Graphene；Knot
Closing scanning electron microscope and transmission electron microscope test understands, the structure of micro crystal graphite alkene is sheet knot
Structure, size in tens nanometers to hundreds of nanometer, atomic force microscope test show the thickness of lamella 1～
3nm, the test of x-ray photoelectron power spectrum shows that the itrogen content of getter with nitrogen doped of Graphene is 1.65%.
Embodiment 4
The first step, weigh the micro crystal graphite 100g that purity is 88%；
Second step, load weighted micro crystal graphite is transferred in the magnetic boat of cleaning (magnetic boat width: 2cm, long: 5cm),
With the heating rates of 10 DEG C/min, temperature is increased to 1000 DEG C, and maintains 10 minutes；
3rd step, while hot micro crystal graphite is transferred in the Dewar flask of 50mL liquid nitrogen；
4th step, treat liquid nitrogen volatilization completely, the micro crystal graphite processed through high temperature and quenching is transferred to 250mL
Can substitute in the ball grinder of gas；
5th step, diameter is respectively the steel ball 3 of 2cm, the steel ball of 1.2cm 12, the steel of 0.6cm
8, pearl is placed in above ready ball grinder；
6th step, encapsulation ball grinder, after ball grinder evacuation, be filled with nitrogen atmosphere, then evacuation, be filled with
Nitrogen atmosphere, is so repeated 3 times；
7th step, the ball grinder that will be filled with nitrogen are fixed on comprehensive ball milling instrument, ball under the frequency of 30Hz
Mill 100h.
The product obtained is detected, at 1350cm in Raman collection of illustrative plates-1And 1590cm-1Place occurs in that graphite
The characteristic peak of alkene, by X-ray powder diffraction test figure it can be seen that the characteristic peak (26 °) of micro crystal graphite is sent out
Give birth to skew, about about 23 ° appearance, illustrated that, in mechanical milling process, micro crystal graphite becomes Graphene；Knot
Closing scanning electron microscope and transmission electron microscope test understands, the structure of micro crystal graphite alkene is sheet knot
Structure, size in tens nanometers to hundreds of nanometer, atomic force microscope test show the thickness of lamella 1～
3nm, the test of x-ray photoelectron power spectrum shows that the itrogen content of getter with nitrogen doped of Graphene is 1.75%.
Embodiment 5
The first step, weigh the micro crystal graphite 140g that purity is 86%；
Second step, load weighted micro crystal graphite is transferred in the magnetic boat of cleaning (magnetic boat width: 2cm, long: 5cm),
With the heating rates of 10 DEG C/min, temperature is increased to 1000 DEG C, and maintains 7 minutes；
3rd step, while hot micro crystal graphite is transferred in the Dewar flask of 100mL liquid nitrogen；
4th step, treat liquid nitrogen volatilization completely, the micro crystal graphite processed through high temperature and quenching is transferred to 250mL
Can substitute in the ball grinder of gas；
5th step, diameter is respectively the steel ball 3 of 2cm, the steel ball of 1.2cm 4, the steel ball of 0.6cm
12 are placed in above ready ball grinder；
6th step, encapsulation ball grinder, after ball grinder evacuation, be filled with nitrogen atmosphere, then evacuation, be filled with
Nitrogen atmosphere, is so repeated 2 times；
7th step, the ball grinder that will be filled with nitrogen are fixed on comprehensive ball milling instrument, ball under the frequency of 40Hz
Mill 80h.
The product obtained is detected, at 1350cm in Raman collection of illustrative plates-1And 1590cm-1Place occurs in that graphite
The characteristic peak of alkene, by X-ray powder diffraction test figure it can be seen that the characteristic peak (26 °) of micro crystal graphite is sent out
Give birth to skew, about about 23 ° appearance, illustrated that, in mechanical milling process, micro crystal graphite becomes Graphene；Knot
Closing scanning electron microscope and transmission electron microscope test understands, the structure of micro crystal graphite alkene is sheet knot
Structure, size in tens nanometers to hundreds of nanometer, atomic force microscope test show the thickness of lamella 1～
3nm, the test of x-ray photoelectron power spectrum shows that the itrogen content of getter with nitrogen doped of Graphene is 1.78%.
Embodiment 6
The first step, weigh the micro crystal graphite 180g that purity is 88%；
Second step, load weighted micro crystal graphite is transferred in the magnetic boat of cleaning (magnetic boat width: 2cm, long: 5cm),
With the heating rates of 10 DEG C/min, temperature is increased to 800 DEG C, and maintains 10 minutes；
3rd step, while hot micro crystal graphite is transferred in the Dewar flask of 90mL liquid nitrogen；
4th step, treat liquid nitrogen volatilization completely, the micro crystal graphite processed through high temperature and quenching is transferred to substitute
In the ball grinder of gas；
5th step, diameter is respectively the steel ball 3 of 2cm, the steel ball of 1.2cm 9, the steel ball of 0.6cm
10 are placed in above ready ball grinder；
6th step, encapsulation ball grinder, after ball grinder evacuation, be filled with nitrogen atmosphere, then evacuation, be filled with
Nitrogen atmosphere, is so repeated 3 times；
7th step, the ball grinder that will be filled with nitrogen are fixed on comprehensive ball milling instrument, ball under the frequency of 50Hz
Mill 120h.The product obtained is detected, at 1350cm in Raman collection of illustrative plates-1And 1590cm-1Place occurs
The characteristic peak of Graphene, by X-ray powder diffraction test figure it can be seen that the characteristic peak of micro crystal graphite
(26 °) there occurs skew, about about 23 ° appearance, illustrates that, in mechanical milling process, micro crystal graphite becomes
Graphene；Test in conjunction with scanning electron microscope and transmission electron microscope and understand, the structure of micro crystal graphite alkene
Being laminar structured, size shows lamella in tens nanometers to hundreds of nanometer, atomic force microscope test
Thickness 1～3nm, the test of x-ray photoelectron power spectrum shows that the itrogen content of getter with nitrogen doped of Graphene is 1.72%.
8th step, the 7th step is obtained product negative pole as Li battery after 120 DEG C of drying and processings, assemble
Become the button cell that diameter is about 2cm, and its capacity character and recursive nature are tested.At 0.1A/g
Testing under electric current, battery capacity is stable at about 600mAh/g, and when being recycled to 100 times, capacity does not has yet
Significantly reduce (Fig. 4), from multiplying power test, when electric current is raised to 1500mAh/g when, battery
Capacity stable at about 500mAh/g, battery is under the conditions of high current density (20A/g), and capacity remains to
Reach about 100mAh/g (Fig. 5).Illustrating at higher current densities, battery completes a charge and discharge process
Only need 18 seconds, i.e. this material has fast charging and discharging feature, and high rate performance is outstanding.Cell assembling processes is at hands
Completing in casing, test system is LAND CT2001A.
Above-described detailed description of the invention, is carried out the purpose of the present invention, technical scheme and beneficial effect
Further describe in detail, be it should be understood that the specific embodiment that the foregoing is only the present invention,
The protection domain being not intended to limit the present invention, within all spirit in the present invention and principle, that is done is any
Amendment, equivalent, improvement etc., should be included within the scope of the present invention.
Claims (3)
1. the method that a ball milling prepares micro crystal graphite alkene, it is characterised in that the preparation of the method
Process comprises the steps:
Step one, by microlite powdered ink with the ramp of 10 DEG C/min to 800～1200 DEG C,
It is incubated 5～10 minutes；
Step 2: the microlite powdered ink after step one heat treatment is transferred to the cleaning equipped with liquid nitrogen
In container, stand and treat liquid nitrogen volatilization completely；
Step 3: the microlite powdered ink obtained in step 2 is transferred to substitute the ball milling of gas
In tank, and steel ball is joined in ball grinder；
Step 4: encapsulated by the ball grinder of step 3, then repeats ball grinder first to take out very
Empty refilling enters the operation more than totally 3 times of nitrogen；
Step 5: the ball grinder described in step 4 is fixed on comprehensive ball milling instrument, 30～
Ball milling 80～120 hours under the frequency of 50Hz, obtain the stratiform crystallite that thickness is 1～3nm
Graphene, the most described micro crystal graphite alkene.
The method that a kind of ball milling the most as claimed in claim 1 prepares micro crystal graphite alkene, its feature exists
In, in step 2, the usage amount of liquid nitrogen is the microlite powdered ink that every 100g step one is initially added
Correspondence at least 50ml liquid nitrogen.
The method that a kind of ball milling the most as claimed in claim 1 prepares micro crystal graphite alkene, its feature exists
In, in step 3, the addition of steel ball is the microlite powdered ink that every 100g step one is initially added
At least 10 steel balls of correspondence.
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| CN105062219A (en) * | 2015-09-14 | 2015-11-18 | 北京理工大学 | Microcrystalline graphene conductive ink and preparation method |
| US10850496B2 (en) * | 2016-02-09 | 2020-12-01 | Global Graphene Group, Inc. | Chemical-free production of graphene-reinforced inorganic matrix composites |
| US9899672B2 (en) * | 2016-05-17 | 2018-02-20 | Nanotek Instruments, Inc. | Chemical-free production of graphene-encapsulated electrode active material particles for battery applications |
| CN106185883B (en) * | 2016-06-27 | 2018-12-18 | 刘效伟 | A kind of method of rapid, high volume production graphene |
| CN106185884B (en) * | 2016-06-27 | 2018-11-27 | 刘效伟 | A kind of method of rapid, high volume production graphene |
| CN107697902A (en) * | 2017-09-29 | 2018-02-16 | 中国石油大学(北京) | A kind of double-doped class graphene nano carbon material of boron nitrogen and preparation method and application |
| CN107555425A (en) * | 2017-10-31 | 2018-01-09 | 湖南国盛石墨科技有限公司 | A kind of micro crystal graphite high temperature pre-processes alkali acid system method of purification |
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| CN103570004A (en) * | 2012-07-25 | 2014-02-12 | 中国科学院大连化学物理研究所 | Simple large-scale preparation and functionalization method of graphene |
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