CN104505512A - Method for preparing microcrystalline graphene through ball milling - Google Patents
Method for preparing microcrystalline graphene through ball milling Download PDFInfo
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- CN104505512A CN104505512A CN201410690141.0A CN201410690141A CN104505512A CN 104505512 A CN104505512 A CN 104505512A CN 201410690141 A CN201410690141 A CN 201410690141A CN 104505512 A CN104505512 A CN 104505512A
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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 cheaply only have 1/3rd of crystalline flake graphite, have the wide market space.Such as, but because technological development drops into not, be very short of the research of micro crystal graphite, prepare micro crystal graphite alkene by micro crystal graphite and then prepare other functional material, the possibility of lithium ion battery negative material is not paid attention to fully.
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 use 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 involves some exacting terms and low productive rate, such as: the carbon fiber preparing N doping under the condition of high-temperature calcination and highly basic activation, the nanometer carbon of 800 DEG C of growths between layered hydroxide, take nano-calcium carbonate as the porous carbon that template high-temperature calcination gelatin obtains, take imidazoles as carbon source, the carbon pipe of Bamboo-shaped is grown, with SiO under 850 DEG C of conditions
2nanosphere is template, and high-temperature calcination egg obtains the porous carbon of porous N doping.These preparation process need to use poisonous chemical reagent in general, need multiple loaded down with trivial details step, consume considerable time, and yielding poorly of obtaining, so that the overall high cost of negative material, be difficult to accomplish scale production.
Summary of the invention
Not good 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; cause total cost too high; be difficult to the problem of accomplishing scale production, by carrying out processing modified to cheap micro crystal graphite, the present invention proposes a kind of method that ball milling prepares micro crystal graphite alkene; the method technique is simply applicable to large-scale production, and obtained micro crystal graphite alkene can be used for the negative material preparing lithium ion battery.
Described method comprises the steps:
Step one, by micro crystal graphite with ramp to 800 ~ 1200 DEG C of 10 DEG C/min, be incubated 5 ~ 10 minutes;
Step 2: the micro crystal graphite after step one heat treated is transferred to and is equipped with in the clean container of liquid nitrogen, every 100g micro crystal graphite correspondence at least 50ml liquid nitrogen, leaves standstill and treats liquid nitrogen volatilization completely;
Step 3: the micro crystal graphite obtained in step 2 is transferred to and can substitutes in the ball grinder of gas, and with the ratio of 20 steel balls corresponding 200g microlite ink powder, steel ball is joined in ball grinder;
Step 4: encapsulated by the ball grinder of step 3, after being vacuumized by ball grinder, is filled with nitrogen atmosphere, so repeats more than 3 times;
Step 5: be fixed on by the ball grinder described in step 4 on comprehensive ball milling instrument, ball milling 80 ~ 120 hours under the frequency of 30 ~ 50Hz, obtains the stratiform micro crystal graphite alkene that described thickness is 1 ~ 3nm.
Beneficial effect
(1) the present invention uses a kind of method of simple possible to prepare micro crystal graphite alkene, and heating and quench process can make micro crystal graphite more easily peel off layered graphene film fast, and the method technique is simple, environmental friendliness.
(2) the raw material micro crystal graphite that the present invention utilizes directly can be obtained by micro crystal graphite ore deposit, and wide material sources are cheap, can produce in enormous quantities for industrialization.
(3) the N doping micro crystal graphite alkene of small pieces that the method for the invention obtains is sheet, have the advantages that volume is fluffy, quality is light, specific area is large, due to the doping of nitrogen-atoms, the energy level of carbon structure there occurs change, be suitable for preparing that capacity is high, the ion cathode material lithium of good rate capability, also can be used as efficient energy conversion and storage material, make up the deficiency applied 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 often needs through high temperature, the step that purifying etc. are loaded down with trivial details, and the method for the invention does not need through these processes, greatly reduce the use cost of micro crystal graphite, extend its range of application.Both protect environment, create economic benefit again.
(5) the method for the invention is owing to introducing doping nitrogen-atoms, and avtive spot is increased, and can have good recursive nature and exceed the capacity of general material with carbon element as lithium cell cathode material.
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 tests the Capacity Plan that micro crystal graphite alkene of the present invention makees the battery of negative material under 0.1A/g electric current in embodiment 6;
Fig. 5 be in embodiment 6 under different electric current (0.1A/g to 45A/g), test the high rate performance figure that micro crystal graphite alkene of the present invention makees negative material battery.
Embodiment
The present invention proposes a kind of straightforward procedure preparing lithium ion battery negative material, and the raw material sources of described method are very extensive, cheap and easy to get, and preparation process is simple, environmental friendliness, low, the applicable large-scale production of cost.Adopting the ion cathode material lithium that described method prepares---the micro crystal graphite alkene of N doping is sheet, has the advantages that volume is fluffy, quality is light, specific area is large.Due to the doping of nitrogen-atoms, the energy level of carbon structure there occurs change, makes micro crystal graphite alkene have potential application as energy and material, is suitable for preparing that capacity is high, the ion cathode material lithium of good rate capability, substantially increases the added value of micro crystal graphite.
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail, but be not limited thereto.
Embodiment 1
The first step, take the micro crystal graphite 200g that purity is 80%;
Second step, load weighted micro crystal graphite transferred in clean magnetic boat (magnetic boat is wide: 2cm, long: 5cm), with the heating rate of 10 DEG C/min, temperature to be increased to 800 DEG C, and to maintain 5 minutes;
3rd step, while hot micro crystal graphite is transferred in the Dewar bottle of 100mL liquid nitrogen;
4th step, treat liquid nitrogen volatilization completely, the micro crystal graphite through high temperature and quenching process is transferred to 250mL and 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 ball 12 of 0.6cm is placed in above ready ball grinder;
6th step, encapsulation ball grinder, after being vacuumized by ball grinder, be filled with nitrogen atmosphere, then vacuumize, be filled with nitrogen atmosphere, so repeat 2 times;
7th step, the ball grinder being full of nitrogen is fixed on comprehensive ball milling instrument, ball milling 80h under the frequency of 30Hz.
The product obtained is detected, at 1350cm in the Raman collection of illustrative plates of Fig. 1
-1and 1590cm
-1having there is the characteristic peak of Graphene in place, can see that the characteristic peak (26 °) of micro crystal graphite there occurs skew, about 23 ° appearance, illustrate that, in mechanical milling process, micro crystal graphite becomes Graphene by X-ray powder diffraction resolution chart; In conjunction with scanning electron microscopy and transmission electron microscope test (as shown in Figures 2 and 3) known, the structure of micro crystal graphite alkene is laminar structured, size is not in tens nanometers to hundreds of nanometer etc., atomic force microscope test shows that the thickness of lamella is at 1 ~ 3nm, and the itrogen content of getter with nitrogen doped of the bright Graphene of x-ray photoelectron power spectrum test chart is 1.7%.
Embodiment 2
The first step, take the micro crystal graphite 180g that purity is 84%;
Second step, load weighted micro crystal graphite transferred in clean magnetic boat (magnetic boat is wide: 2cm, long: 5cm), with the heating rate of 10 DEG C/min, temperature to be increased to 1200 DEG C, and to maintain 10 minutes;
3rd step, while hot micro crystal graphite is transferred in the Dewar bottle of 100mL liquid nitrogen;
4th step, treat liquid nitrogen volatilization completely, the micro crystal graphite through high temperature and quenching process is transferred to and 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 6, the steel ball 10 of 0.6cm is placed in above ready ball grinder;
6th step, encapsulation ball grinder, after being vacuumized by ball grinder, be filled with nitrogen atmosphere, then vacuumize, be filled with nitrogen atmosphere, so repeat 3 times;
7th step, the ball grinder being full of nitrogen is fixed on comprehensive ball milling instrument, ball milling 120h under the frequency of 50Hz.
The product obtained is detected, at 1350cm in Raman collection of illustrative plates
-1and 1590cm
-1having there is the characteristic peak of Graphene in place, can see that the characteristic peak (26 °) of micro crystal graphite there occurs skew, greatly about about 23 ° appearance, illustrate that, in mechanical milling process, micro crystal graphite becomes Graphene by X-ray powder diffraction resolution chart; Test known in conjunction with scanning electron microscopy and transmission electron microscope, the structure of micro crystal graphite alkene is laminar structured, size is not in tens nanometers to hundreds of nanometer etc., atomic force microscope test shows that the thickness of lamella is at 1 ~ 3nm, and the itrogen content of getter with nitrogen doped of the bright Graphene of x-ray photoelectron power spectrum test chart is 1.6%.
Embodiment 3
The first step, take the micro crystal graphite 140g that purity is 80%;
Second step, load weighted micro crystal graphite transferred in clean magnetic boat (magnetic boat is wide: 2cm, long: 5cm), with the heating rate of 10 DEG C/min, temperature to be increased to 900 DEG C, and to maintain 7 minutes;
3rd step, while hot micro crystal graphite is transferred in the Dewar bottle of 80mL liquid nitrogen;
4th step, treat liquid nitrogen volatilization completely, the micro crystal graphite through high temperature and quenching process is transferred to 250mL and 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 ball 8 of 0.6cm is placed in above ready ball grinder;
6th step, encapsulation ball grinder, after being vacuumized by ball grinder, be filled with nitrogen atmosphere, then vacuumize, be filled with nitrogen atmosphere, so repeat 2 times;
7th step, the ball grinder being full of nitrogen is fixed on comprehensive ball milling instrument, ball milling 120h under the frequency of 30Hz.
The product obtained is detected, at 1350cm in Raman collection of illustrative plates
-1and 1590cm
-1having there is the characteristic peak of Graphene in place, can see that the characteristic peak (26 °) of micro crystal graphite there occurs skew, greatly about about 23 ° appearance, illustrate that, in mechanical milling process, micro crystal graphite becomes Graphene by X-ray powder diffraction resolution chart; Test known in conjunction with scanning electron microscopy and transmission electron microscope, the structure of micro crystal graphite alkene is laminar structured, size is not in tens nanometers to hundreds of nanometer etc., atomic force microscope test shows that the thickness of lamella is at 1 ~ 3nm, and the itrogen content of getter with nitrogen doped of the bright Graphene of x-ray photoelectron power spectrum test chart is 1.65%.
Embodiment 4
The first step, take the micro crystal graphite 100g that purity is 88%;
Second step, load weighted micro crystal graphite transferred in clean magnetic boat (magnetic boat is wide: 2cm, long: 5cm), with the heating rate of 10 DEG C/min, temperature to be increased to 1000 DEG C, and to maintain 10 minutes;
3rd step, while hot micro crystal graphite is transferred in the Dewar bottle of 50mL liquid nitrogen;
4th step, treat liquid nitrogen volatilization completely, the micro crystal graphite through high temperature and quenching process is transferred to 250mL and 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 ball 8 of 0.6cm is placed in above ready ball grinder;
6th step, encapsulation ball grinder, after being vacuumized by ball grinder, be filled with nitrogen atmosphere, then vacuumize, be filled with nitrogen atmosphere, so repeat 3 times;
7th step, the ball grinder being full of nitrogen is fixed on comprehensive ball milling instrument, ball milling 100h under the frequency of 30Hz.
The product obtained is detected, at 1350cm in Raman collection of illustrative plates
-1and 1590cm
-1having there is the characteristic peak of Graphene in place, can see that the characteristic peak (26 °) of micro crystal graphite there occurs skew, greatly about about 23 ° appearance, illustrate that, in mechanical milling process, micro crystal graphite becomes Graphene by X-ray powder diffraction resolution chart; Test known in conjunction with scanning electron microscopy and transmission electron microscope, the structure of micro crystal graphite alkene is laminar structured, size is not in tens nanometers to hundreds of nanometer etc., atomic force microscope test shows that the thickness of lamella is at 1 ~ 3nm, and the itrogen content of getter with nitrogen doped of the bright Graphene of x-ray photoelectron power spectrum test chart is 1.75%.
Embodiment 5
The first step, take the micro crystal graphite 140g that purity is 86%;
Second step, load weighted micro crystal graphite transferred in clean magnetic boat (magnetic boat is wide: 2cm, long: 5cm), with the heating rate of 10 DEG C/min, temperature to be increased to 1000 DEG C, and to maintain 7 minutes;
3rd step, while hot micro crystal graphite is transferred in the Dewar bottle of 100mL liquid nitrogen;
4th step, treat liquid nitrogen volatilization completely, the micro crystal graphite through high temperature and quenching process is transferred to 250mL and 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 12 of 0.6cm is placed in above ready ball grinder;
6th step, encapsulation ball grinder, after being vacuumized by ball grinder, be filled with nitrogen atmosphere, then vacuumize, be filled with nitrogen atmosphere, so repeat 2 times;
7th step, the ball grinder being full of nitrogen is fixed on comprehensive ball milling instrument, ball milling 80h under the frequency of 40Hz.
The product obtained is detected, at 1350cm in Raman collection of illustrative plates
-1and 1590cm
-1having there is the characteristic peak of Graphene in place, can see that the characteristic peak (26 °) of micro crystal graphite there occurs skew, greatly about about 23 ° appearance, illustrate that, in mechanical milling process, micro crystal graphite becomes Graphene by X-ray powder diffraction resolution chart; Test known in conjunction with scanning electron microscopy and transmission electron microscope, the structure of micro crystal graphite alkene is laminar structured, size is not in tens nanometers to hundreds of nanometer etc., atomic force microscope test shows that the thickness of lamella is at 1 ~ 3nm, and the itrogen content of getter with nitrogen doped of the bright Graphene of x-ray photoelectron power spectrum test chart is 1.78%.
Embodiment 6
The first step, take the micro crystal graphite 180g that purity is 88%;
Second step, load weighted micro crystal graphite transferred in clean magnetic boat (magnetic boat is wide: 2cm, long: 5cm), with the heating rate of 10 DEG C/min, temperature to be increased to 800 DEG C, and to maintain 10 minutes;
3rd step, while hot micro crystal graphite is transferred in the Dewar bottle of 90mL liquid nitrogen;
4th step, treat liquid nitrogen volatilization completely, the micro crystal graphite through high temperature and quenching process is transferred to and 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 9, the steel ball 10 of 0.6cm is placed in above ready ball grinder;
6th step, encapsulation ball grinder, after being vacuumized by ball grinder, be filled with nitrogen atmosphere, then vacuumize, be filled with nitrogen atmosphere, so repeat 3 times;
7th step, the ball grinder being full of nitrogen is fixed on comprehensive ball milling instrument, ball milling 120h under the frequency of 50Hz.The product obtained is detected, at 1350cm in Raman collection of illustrative plates
-1and 1590cm
-1having there is the characteristic peak of Graphene in place, can see that the characteristic peak (26 °) of micro crystal graphite there occurs skew, greatly about about 23 ° appearance, illustrate that, in mechanical milling process, micro crystal graphite becomes Graphene by X-ray powder diffraction resolution chart; Test known in conjunction with scanning electron microscopy and transmission electron microscope, the structure of micro crystal graphite alkene is laminar structured, size is not in tens nanometers to hundreds of nanometer etc., atomic force microscope test shows that the thickness of lamella is at 1 ~ 3nm, and the itrogen content of getter with nitrogen doped of the bright Graphene of x-ray photoelectron power spectrum test chart is 1.72%.
8th step, the 7th step is obtained product negative pole as Li battery after 120 DEG C of drying and processings, be assembled into the button cell that diameter is about 2cm, and its capacity character and recursive nature are tested.Test under 0.1A/g electric current, battery capacity is stabilized in about 600mAh/g, and capacity does not also significantly reduce (Fig. 4) when being recycled to 100 times, test from multiplying power, when electric current is raised to 1500mAh/g time, the capacity stablizes of battery is at about 500mAh/g, and battery is under high current density (20A/g) condition, and capacity still can reach about 100mAh/g (Fig. 5).Illustrate at higher current densities, battery completes a charge and discharge process and only needs 18 seconds, and namely this material has fast charging and discharging feature, and high rate performance is outstanding.Cell assembling processes completes in glove box, and test macro is LAND CT2001A.
Above-described embodiment; further detailed description has been carried out to object of the present invention, technical scheme and beneficial effect; be understood that; the foregoing is only specific embodiments of the invention; the protection range be not intended to limit the present invention; all within spirit of the present invention and principle, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (3)
1. ball milling prepares a method for micro crystal graphite alkene, it is characterized in that, the preparation process of the method comprises the steps:
Step one, by microlite ink powder with ramp to 800 ~ 1200 DEG C of 10 DEG C/min, be incubated 5 ~ 10 minutes;
Step 2: be transferred to by the microlite ink powder after step one heat treatment and be equipped with in the clean container of liquid nitrogen, leaves standstill and treats liquid nitrogen volatilization completely;
Step 3: the microlite ink powder obtained in step 2 is transferred to and can substitutes in the ball grinder of gas, and steel ball is joined in ball grinder;
Step 4: encapsulated by the ball grinder of step 3, after being vacuumized by ball grinder, is filled with nitrogen atmosphere, so repeats first to vacuumize the operation more than 2 times being filled with nitrogen again;
Step 5: be fixed on by the ball grinder described in step 4 on comprehensive ball milling instrument, ball milling 80 ~ 120 hours under the frequency of 30 ~ 50Hz, obtains the stratiform micro crystal graphite alkene that thickness is 1 ~ 3nm, i.e. described micro crystal graphite alkene.
2. a kind of ball milling prepares the method for micro crystal graphite alkene as claimed in claim 1, it is characterized in that, in step 2, the use amount of liquid nitrogen is that the microlite ink powder that every 100g step one initially adds corresponds to few 50ml liquid nitrogen.
3. a kind of ball milling prepares the method for micro crystal graphite alkene as claimed in claim 1, it is characterized in that, in step 3, the addition of steel ball is that the microlite ink powder that every 100g step one initially adds corresponds to few 10 steel balls.
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| CN108778994A (en) * | 2016-02-09 | 2018-11-09 | 纳米技术仪器公司 | The inorganic matrix composite of graphene enhancing is produced without chemicals formula |
| CN109155399A (en) * | 2016-05-17 | 2019-01-04 | 纳米技术仪器公司 | The electrode active material particles that graphene for battery applications is encapsulated are produced without chemicals formula |
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