CN107814383A - A kind of lithium ion battery modification of microcrystalline graphite cathode material and its production and use - Google Patents
A kind of lithium ion battery modification of microcrystalline graphite cathode material and its production and use Download PDFInfo
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- CN107814383A CN107814383A CN201710898456.8A CN201710898456A CN107814383A CN 107814383 A CN107814383 A CN 107814383A CN 201710898456 A CN201710898456 A CN 201710898456A CN 107814383 A CN107814383 A CN 107814383A
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- crystal graphite
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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
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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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 present invention relates to carbon negative electrode material of lithium ion cell technical field, and in particular to a kind of lithium ion battery modification of microcrystalline graphite cathode material and its production and use.Prepared material has some following advantage：(1) present invention is prepared for the natural graphite negative electrode material that Delanium original position is embedded in the modification with core shell structure on inside native graphite and surface, retain the overall structure characteristic of natural micro crystal graphite, and Delanium is filled in the pore interior of natural micro crystal graphite, and it is coated on outer surface.(2) compared with existing negative material, the negative material isotropism prepared by the inventive method is good, suppresses to absorb expansion caused by electrode in charge and discharge process；Material initial coulomb efficiency prepared by the present invention is high, and service life length, high-rate charge-discharge capability is good, Delanium can be replaced to make power battery cathode material, so as to substantially reduce cost.(3) this method preparation technology is simple, and cost is cheap, has higher practicality.
Description
Technical field
The present invention relates to carbon negative electrode material of lithium ion cell technical field, is modified more particularly to a kind of lithium ion battery
Micro crystal graphite negative material and its production and use.
Background technology
Lithium ion battery has a series of advantages such as specific capacity height, operating voltage height, the good, memory-less effect of security,
It is widely used in the fields such as 3C Product, power set and energy storage device.With the popularization of new-energy automobile, its application has been opened up
Open up the fields such as electric car, automobile.In recent years, with electronic product and it is vehicle-mounted with energy storage device to miniaturization, lightweight and more
The requirement of function, for a long time drivingization improves constantly, to lithium ion battery high-energy-density, high rate capability and long circulating longevity
The requirement of life is constantly lifted.
Negative material plays key effect as one of battery core part to battery combination property.Commercialization at present
The negative material of lithium ion battery is still that graphite type material is occupied an leading position, although Delanium good cycle, its
Body capacity is low, expensive, adds the manufacturing cost of electrokinetic cell.It is native graphite Yin Qigao charge/discharge capacity, good
Charge and discharge platform, wide material sources, cost is low and is used widely.But conventional modified natural crystalline flake graphite crystallization it is complete,
Aspect orientation is flourishing, anisotropy is obvious, border of the permission lithium ion along graphite is embedded and abjection, causes Lithium-ion embeding to take off
Go out distance, unsuitable large current charge discharges, fast charging and discharging performance is poor.These defects limit modified natural scale stone
Black further applying in high performance lithium ion battery.Natural micro crystal graphite is a kind of mineral products of China's rich reserves, it
Crystal is small, the structure of nearly isotropy causes there is pole at cycle life, the aspect of fast charging and discharging two with the negative material of its preparation
For excellent performance.But natural micro crystal graphite impurity content is high, and carbon content is only 80~90%, and is used as negative electrode of lithium ion battery
Material, the purity of graphite must be increased to more than 99.0%.CN1063958A and CN105977487A is using crushing, pitch bag
Cover, be carbonized, graphitization prepares modification of microcrystalline graphite cathode material, removed using high temperature graphitization inside natural micro crystal graphite
Impurity, after impurity removes, a large amount of micropores can be left inside micro crystal graphite, first charge-discharge efficiency can be caused low and circulate the longevity
Order the defects of short.
The content of the invention
To improve above mentioned problem, it is an object of the invention to provide a kind of lithium ion battery modification of microcrystalline graphite cathode material
And its production and use.
The present invention provides a kind of preparation method of the micro crystal graphite negative material of modification, the described method comprises the following steps：
(1) by micro crystal graphite coarse crushing, then purified with acidic aqueous solution；
(2) crushing material that obtains step (1), shaping, classification；
(3) material that step (2) obtains is fitted into packaging bag and sealed, packaging bag is put into impregnating autoclave, vacuumized, and added
Hot submersion tank；
(4) pitch of liquid is injected into impregnating autoclave under high pressure, when asphaltic liquid exceedes the packaging bag height in impregnating autoclave,
Stopping vacuumizes, and pressure-maintaining and heat-preservation is for a period of time；
(5) after step (4) insulation terminates, pitch is excluded from impregnating autoclave, and returns to molten groove and recycles, it is to be packaged
After bag takes out cooling, obtained material is crushed, washed, filtering, drying；
(6) material for obtaining step (5) carries out carbonization treatment；
(7) material for obtaining step (6) carries out graphitization processing, obtains the natural micro crystal graphite negative material of modification.
According to the present invention, the phosphorus content of micro crystal graphite can be 80~90% in step (1)；
According to the present invention, step (1) can be carried out in a heated condition, such as temperature is 85~95 DEG C；
According to the present invention, in step (1), described acidic aqueous solution is selected from the inorganic acid of one or more arbitrary proportions
Mixed aqueous solution, the inorganic acid such as HCl, HF, H2SO4、H2S2O7、H3PO4Or HNO3, such as H2SO4, HF and HCl nitration mixture water
Solution；
According to the present invention, in step (1), micro crystal graphite purity brings up to more than 99.0%；
According to the present invention, in step (2), it is micro- that described pulverizer is selected from low velocity impact formula nodularization pulverizer, stream swirl
Powder machine, micronizer or ultra micro ball mill；Described trimmer is selected from airslide disintegrating mill, high pressure pulverizer or bar type machinery powder
Broken machine；Described grader is selected from gas flow sizing machine, jetting type grader, submicron grader or ultra micro rice gas flow sizing machine；
According to the present invention, in step (2), the D of material after described crushing, shaping, classification50It can be 8~20 μm；
According to the present invention, in step (3), described impregnating autoclave vacuum can be 0.07~0.09MPa；
According to the present invention, in step (3), described heating-up temperature can be 300~350 DEG C；
According to the present invention, in step (3), described packaging can be soft package；
According to the present invention, in step (4), described pitch be selected from impregnating pitch or softening point be 65~85 DEG C, quinoline not
Molten thing content is less than 1% pitch；
According to the present invention, in step (4), described high pressure can be 30MPa~50MPa, and soaking time can be 1~3
Hour；
According to the present invention, in step (4), described molten bath temperature degree can be 300~350 DEG C；
According to the present invention, broken described in step (5) be the crushing material that will be obtained into coarse powder, its particle diameter can be 0.5
~5mm；
According to the present invention, the washing in step (5) can use organic solvent washing；
According to the present invention, disintegrating machine used any can be realized to be well known in the prior art in step (1) and (5)
The broken device of the material, it is selected from turbine type crushing machine, machine, Raymond machine etc. are broken in Hubei Province；
According to the present invention, in step (5), described organic solvent is selected from washing oil, kerosene, benzene analog derivative, oleic acid, quinoline
In one or more；
According to the present invention, in step (5), described washing is preferably carried out under condition of heating and stirring；Preferably, it is described to add
The temperature of heat can be 60~120 DEG C, and the speed of the stirring can be 200~700r/min, for example, 300~500r/
min；
According to the present invention, in step (5), described washing times and wash time do not limit specifically, will can wrap
The unnecessary pitch for overlaying on its surface cleans up, and washing times are 1~3 time to example as mentioned, and described wash time is 5
~10 hours；
According to the present invention, in step (5), described drying can be under vacuum in 160~200 DEG C of progress；
According to the present invention, in step (6), the temperature of described carbonization treatment is preferably 800~1200 DEG C, described carbon
The change time is preferably 4~10 hours；
According to the present invention, in step (6), it is necessary to repeat during micro crystal graphite filling rate ＜ 98% after described carbonization treatment
Step (3), (4), (5), (6)；
According to the present invention, in step (7), described graphitization processing method and condition can be at the ordinary graphite of this area
The method and condition of reason, the temperature of described graphitization processing are preferably 2800~3000 DEG C；
The present invention also provides a kind of natural micro crystal graphite negative material of modification, the modification day being prepared by the above method
Right micro crystal graphite negative material；
According to the present invention, the D of the material50For 9~21 μm.
Present invention also offers a kind of natural micro crystal graphite negative material of modification, the natural micro crystal graphite of the modification is born
Pole material has core shell structure, and the core is the native graphite that Delanium is filled with hole, and the shell is Delanium；
According to the present invention, filling rate >=98% of Delanium in the natural micro crystal graphite hole；
According to the present invention, the D of the negative material50For 9~21 μm；
According to the present invention, the mass fraction that Delanium accounts for negative material in the negative material is 7~10%, more preferably
For 8%；
According to the present invention, the tap density of the negative material is 1.1~1.25g/cm3。
The present invention also provides a kind of purposes of the natural micro crystal graphite negative material of above-mentioned modification, and it is used to prepare lithium ion
The negative pole of electrokinetic cell.
The present invention also provides a kind of negative pole of lithium-ion-power cell, and it includes the natural micro crystal graphite of above-mentioned modification and born
Pole material.
The present invention also provides a kind of lithium-ion-power cell, and it includes the negative pole of above-mentioned lithium-ion-power cell.
Beneficial effect
(1) present invention can ensure pitch in liquid completely at high temperature under high pressure to natural micro crystal graphite powder infusion pitch
The hole inside graphite particle is filled under state, while pitch-coating layer is formed on its surface, after graphitization, obtains Delanium
Original position is embedded in the natural graphite negative electrode material of the modification with core shell structure on inside native graphite and surface, retains natural micro-
The overall structure characteristic of spar ink, and Delanium is filled in the pore interior of natural micro crystal graphite, and it is coated on appearance
Face.Filling rate >=98% of Delanium in native graphite hole, particle surface is smooth, and spheroidization degree is high.
(2) natural graphite negative electrode material of the modification prepared by the inventive method is compared with existing negative material, respectively to
The same sex is good, suppresses to absorb expansion, expansion rate≤6% caused by electrode in charge and discharge process；Discharge capacity >=365mAh/g, first
Coulombic efficiency >=96%, cycle life are significantly improved.Room temperature 1C circulates 2000 weeks capability retention >=87%, especially in height
During rate charge-discharge, the cycle performance of whole material significantly improves, and high current (3C~5C) charge-discharge performance is good, capability retention
>=86%, it is seen then that the material initial coulomb efficiency prepared by the present invention is high, and service life length, high-rate charge-discharge capability is good, can
To replace Delanium to make power battery cathode material, so as to substantially reduce cost.
(3) this method preparation technology is simple, and cost is cheap, has higher practicality.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limit the scope of the invention.Furthermore, it is to be understood that after content disclosed in this invention has been read, ability
Field technique personnel can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the protection that the present invention is limited
Within the scope of.
Embodiment 1
(1) the micro crystal graphite coarse powder of phosphorus content 85% is broken to 100 mesh, then uses H at 95 DEG C2SO4:HF:HCl(1:2:
1.5) the nitration mixture aqueous solution purifies, and micro crystal graphite purity brings up to 99.0%；
(2) material of step (1) is first crushed with low velocity impact formula nodularization pulverizer, then with airslide disintegrating mill shaping, most
Air current classifying is used afterwards, obtains D50For 8 μm of material；
(3) material that step (2) obtains is fitted into soft packaging bag and sealed, packaging bag is put into impregnating autoclave, vacuumized,
Hot submersion tank, makes its vacuum reach 0.07MPa, and temperature reaches 300 DEG C.
(4) impregnating autoclave of the pitch implantation step (3) in molten groove (350 DEG C) is impregnated when asphaltic liquid exceedes under 30MPa
During packaging bag height in tank, stop vacuumizing, 1 hour is incubated under 40MPa；
(5) after step (4) insulation terminates, pitch is excluded from impregnating autoclave, and returns to molten groove and recycles, is treated soft
After cooling is taken out in packaging bag, obtained material is broken into 3mm coarse powder in Raymond machine, obtained coarse powder is put into 60 DEG C of coal
In oil, after being stirred 3 hours with 300r/min speed, filtering, filtrate is relaundered 1 time, in 160 DEG C of bakings under vacuum condition
It is dry.
(6) material for obtaining step (5) under nitrogen protection, and carbonization treatment 5 hours at a temperature of 1300 DEG C, cooling
To room temperature.
(7) material for obtaining step (6) carries out the processing 3 hours of (2800 DEG C) of graphitizable high temperature, obtains the natural of modification
Micro crystal graphite negative material.
Embodiment 2
(1) the micro crystal graphite coarse powder of phosphorus content 90% is broken to 100 mesh, then uses H at 90 DEG C2SO4:HF:HCl(1:
1.5:1) the nitration mixture aqueous solution purifies, and micro crystal graphite purity brings up to 99.2%；
(2) material of step (1) is first crushed with stream swirl pulverizing mill, then with high pressure pulverizer shaping, finally used
Jetting type grader, obtains D50For 12 μm of material；
(3) material that step (2) obtains is fitted into soft packaging bag and sealed, packaging bag is put into impregnating autoclave, vacuumized,
Hot submersion tank, makes its vacuum reach 0.08MPa, and temperature reaches 300 DEG C.
(4) impregnating autoclave of the pitch implantation step (3) in molten groove (300 DEG C) is impregnated when asphaltic liquid exceedes under 50MPa
During packaging bag height in tank, stop vacuumizing, 2 hours are incubated under 50MPa；
(5) after step (4) insulation terminates, pitch is excluded from impregnating autoclave, and returns to molten groove and recycles, is treated soft
After cooling is taken out in packaging bag, obtained material is broken into 2mm coarse powder in turbine type crushing machine, obtained coarse powder is put into
In 120 DEG C of dimethylbenzene, after being stirred 2 hours with 500r/min speed, filtering.Filtrate is relaundered 2 times, vacuum condition
Under in 200 DEG C drying.
(6) material for obtaining step (5) under nitrogen protection, and carbonization treatment 8 hours at a temperature of 1000 DEG C, cooling
To room temperature.
(7) material for obtaining step (6) carries out the processing 5 hours of (2800 DEG C) of graphitizable high temperature, obtains the natural of modification
Micro crystal graphite negative material.
Embodiment 3
(1) the micro crystal graphite coarse powder of phosphorus content 80% is broken to 100 mesh, then uses H at 95 DEG C2SO4:HF:HCl(1:
2.5:2) the nitration mixture aqueous solution purifies, and micro crystal graphite purity brings up to 99.4%；
(2) material of step (1) is first crushed with micronizer, then with bar type mechanical crusher, finally using ultra micro
Rice gas flow sizing machine, obtains D50For 16 μm of material；
(3) material that step (2) obtains is fitted into soft packaging bag and sealed, packaging bag is put into impregnating autoclave, vacuumized,
Hot submersion tank, makes its vacuum reach 0.09MPa, and temperature reaches 330 DEG C.
(4) impregnating autoclave of the pitch implantation step (3) in molten groove (330 DEG C) is impregnated when asphaltic liquid exceedes under 50MPa
During packaging bag height in tank, stop vacuumizing, 3 hours are incubated under 50MPa；
(5) after step (4) insulation terminates, pitch is excluded from impregnating autoclave, and returns to molten groove and recycles, is treated soft
After cooling is taken out in packaging bag, obtained material is broken into 1mm coarse powder in Raymond machine, obtained coarse powder is put into 100 DEG C
In washing oil, after being stirred 2 hours with 400r/min speed, filtering.Filtrate is relaundered 1 time, in 200 DEG C under vacuum condition
Drying.
(6) material for obtaining step (5) under nitrogen protection, and carbonization treatment 8 hours at a temperature of 1200 DEG C, cooling
To room temperature.
(7) material for obtaining step (6) carries out the processing 5 hours of (3000 DEG C) of graphitizable high temperature, obtains the natural of modification
Micro crystal graphite negative material.
Embodiment 4
(1) the micro crystal graphite coarse powder of phosphorus content 85% is broken to 100 mesh, then uses H at 90 DEG C2SO4:HF:HCl(1:
2.5:2) the nitration mixture aqueous solution purifies, and micro crystal graphite purity brings up to 99.0%；
(2) material of step (1) is first crushed with ultra micro ball mill, then with bar type mechanical crusher, finally using sub-micro
Rice grader, obtains D50For 20 μm of material.
(3) material that step (2) obtains is fitted into soft packaging bag and sealed, packaging bag is put into impregnating autoclave, vacuumized,
Hot submersion tank, makes its vacuum reach 0.09MPa, and temperature reaches 320 DEG C.
(4) impregnating autoclave of the pitch implantation step (3) in molten groove (320 DEG C) is impregnated when asphaltic liquid exceedes under 45MPa
During packaging bag height in tank, stop vacuumizing, 3 hours are incubated under 45MPa；
(5) after step (4) insulation terminates, pitch is excluded from impregnating autoclave, and returns to molten groove and recycles, is treated soft
After cooling is taken out in packaging bag, obtained material is broken into 1mm coarse powder in Raymond machine, obtained coarse powder is put into 60 DEG C of coal
In oil, after being stirred 2 hours with 300r/min speed, filtering.Filtrate is relaundered 3 times, in 160 DEG C of bakings under vacuum condition
It is dry.
(6) under nitrogen protection, and carbonization treatment 10 hours at a temperature of 1000 DEG C are cold for the material for obtaining step (5)
But room temperature is arrived.
(7) material for obtaining step (6) carries out the processing 8 hours of (2800 DEG C) of graphitizable high temperature, is prepared modified
Natural micro crystal graphite negative material.
Comparative example 1
(1) the micro crystal graphite coarse powder of phosphorus content 85% is broken to 100 mesh, then uses H at 95 DEG C2SO4:HF:HCl(1:2:
1.5) the nitration mixture aqueous solution purifies, and micro crystal graphite purity brings up to 99.0%；
(2) material of step (1) is first crushed with low velocity impact formula nodularization pulverizer, then with airslide disintegrating mill shaping, most
Air current classifying is used afterwards, obtains D50For 8 μm of material.
(3) material for obtaining step (2) and pitch (quinoline insolubles content 0.5%) in mass ratio 100:30 mixing are equal
It is even, it is fitted into graphite crucible.Graphite crucible is put into Muffle furnace, is warming up to 300 DEG C, after being incubated 3 hours, powers off furnace cooling
To room temperature；
(4) material that step (3) obtains is broken into 3mm coarse powder in Raymond machine, obtained coarse powder is put into 60 DEG C
In kerosene, after being stirred 3 hours with 300r/min speed, filter, in 160 DEG C of drying under vacuum condition.
(5) material for obtaining step (4) under nitrogen protection, and carbonization treatment 5 hours at a temperature of 1300 DEG C, cooling
To room temperature.
(6) material for obtaining step (5) carries out the processing 3 hours of (2800 DEG C) of graphitizable high temperature, is prepared modified
Natural micro crystal graphite negative material.
Comparative example 2
(1) by average grain diameter D50For 20 μm of natural flake graphites, it is fitted into soft packaging bag and seals, packaging bag is put into leaching
Stain tank, is vacuumized, hot submersion tank, its vacuum is reached 0.07MPa, and temperature reaches 300 DEG C.
(2) pitch in molten groove (350 DEG C) is injected into impregnating autoclave under 30MPa, when asphaltic liquid exceedes the bag in impregnating autoclave
When packing height, stop vacuumizing, 1 hour is incubated under 40MPa；
(3) after step (2) insulation terminates, pitch is excluded from impregnating autoclave, and return to molten groove and recycle.Treat soft
After cooling is taken out in packaging bag, obtained material is broken into 3mm coarse powder in Raymond machine, obtained coarse powder is put into 60 DEG C of coal
In oil, after being stirred 3 hours with 300r/min speed, filtering, filtrate is relaundered 1 time, in 160 DEG C of bakings under vacuum condition
It is dry.
(4) material for obtaining step (3) under nitrogen protection, and carbonization treatment 5 hours at a temperature of 1300 DEG C, cooling
To room temperature.
(5) material for obtaining step (4) carries out the processing 3 hours of (2800 DEG C) of graphitizable high temperature, is prepared modified
Natural micro crystal graphite negative material.
Embodiment and comparative example performance test
Respectively Example 1-4, comparative example 1-2 the modification being prepared through graphitization processing natural graphite cathode material
Material, by modified natural graphite negative electrode material：Kynoar (PVDF)：Electrically conductive graphite=93：5：2 mass ratio mixing
Afterwards, it is placed in stirring in high speed dispersor and produces active slurry, is coated to aluminium foil and obtains cathode pole piece.
Assemble to obtain lithium ion battery using above-mentioned cathode pole piece and lithium positive pole, test the head of modified native graphite respectively
Secondary reversible capacity, initial coulomb efficiency, circulation volume conservation rate and electrode expansion rate, concrete outcome are shown in Table 1.
The electrochemical property test result of table 1.
As can be seen from Table 1, there is good cycle performance using the modified natural micro crystal graphite negative material of the present invention
And high rate performance, Delanium can be replaced to make cathode material of lithium-ion power battery.With existing natural graphite cathode material
Material is compared, modified natural graphite negative electrode material initial coulomb efficiency >=96% of the present invention, and room temperature 1C, which circulates 2000 weeks capacity, to be protected
Holdup >=87%, expansion rate≤6%, especially in high power charging-discharging, significantly improve the cycle performance of whole material, big electricity
It is good to flow (3C~5C) charge-discharge performance, capability retention >=86%, it is seen then that the material prepared by the present invention is highly suitable for manufacturing
Lithium-ion-power cell.
More than, embodiments of the present invention are illustrated.But the present invention is not limited to above-mentioned embodiment.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution and improvements done etc., it should be included in the guarantor of the present invention
Within the scope of shield.
Claims (10)
1. the preparation method of the micro crystal graphite negative material of a kind of modification, it is characterised in that comprise the following steps：
(1) by micro crystal graphite coarse crushing, then purified with acidic aqueous solution；
(2) crushing material that obtains step (1), shaping, classification；
(3) material that step (2) obtains is fitted into packaging bag and sealed, packaging bag is put into impregnating autoclave, vacuumized, and heat leaching
Stain tank；
(4) pitch of liquid is injected into impregnating autoclave under high pressure, when asphaltic liquid exceedes the packaging bag height in impregnating autoclave, stopped
Vacuumize, pressure-maintaining and heat-preservation is for a period of time；
(5) after step (4) insulation terminates, pitch is excluded from impregnating autoclave, and returns to molten groove and recycles, bag to be packaged takes
Go out after cooling, obtained material is crushed, wash, filtering, drying；
(6) material for obtaining step (5) carries out carbonization treatment；
(7) material for obtaining step (6) carries out graphitization processing, obtains the natural micro crystal graphite negative material of modification.
2. preparation method as claimed in claim 1, it is characterised in that the phosphorus content of micro crystal graphite can be 80 in step (1)
~90%；
Preferably, step (1) can be carried out in a heated condition, such as temperature is 85~95 DEG C；
Preferably, in step (1), the mixing that described acidic aqueous solution is selected from the inorganic acid of one or more arbitrary proportions is water-soluble
Liquid, the inorganic acid such as HCl, HF, H2SO4、H2S2O7、H3PO4Or HNO3, such as H2SO4, HF and HCl the nitration mixture aqueous solution；
Preferably, in step (1), micro crystal graphite purity brings up to more than 99.0%；
Preferably, in step (2), described pulverizer is selected from low velocity impact formula nodularization pulverizer, stream swirl pulverizing mill, ultra micro
Pulverizer or ultra micro ball mill；Described trimmer is selected from airslide disintegrating mill, high pressure pulverizer or bar type mechanical crusher；It is described
Grader be selected from gas flow sizing machine, jetting type grader, submicron grader or ultra micro rice gas flow sizing machine；
Preferably, in step (2), the D of material after described crushing, shaping, classification50It can be 8~20 μm.
3. preparation method as claimed in claim 1 or 2, it is characterised in that in step (3), described impregnating autoclave vacuum can
Think 0.07~0.09MPa；
Preferably, in step (3), described heating-up temperature can be 300~350 DEG C；
Preferably, in step (3), described packaging can be soft package；
Preferably, in step (4), it is 65~85 DEG C, quinoline insolubles content that described pitch, which is selected from impregnating pitch or softening point,
Pitch less than 1%；
Preferably, in step (4), described high pressure can be 30MPa~50MPa, and soaking time can be 1~3 hour；
Preferably, in step (4), described molten bath temperature degree can be 300~350 DEG C；
Preferably, broken described in step (5) be the crushing material that will be obtained into coarse powder, its particle diameter can be 0.5~5mm；
Preferably, the washing in step (5) can use organic solvent washing；
Preferably, disintegrating machine used in step (1) and (5) any can realize that the material is broken to be well known in the prior art
Broken device, it is selected from turbine type crushing machine, machine, Raymond machine etc. are broken in Hubei Province；
Preferably, in step (5), the one kind of described organic solvent in washing oil, kerosene, benzene analog derivative, oleic acid, quinoline
It is or a variety of；
Preferably, in step (5), described washing is preferably carried out under condition of heating and stirring；Preferably, the temperature of the heating
It can be 60~120 DEG C, the speed of the stirring can be 200~700r/min, for example, 300~500r/min；
Preferably, in step (5), described washing times and wash time do not limit specifically, can will be coated on its table
The unnecessary pitch in face cleans up, and washing times are 1~3 time to example as mentioned, and described wash time is 5~10 small
When；
Preferably, in step (5), described drying can be under vacuum in 160~200 DEG C of progress.
4. the preparation method as described in claim any one of 1-3, it is characterised in that in step (6), described carbonization treatment
Temperature is preferably 800~1200 DEG C, and described carbonization time is preferably 4~10 hours；
In step (6), after described carbonization treatment during micro crystal graphite filling rate ＜ 98%, it is necessary to repeat step (3), (4), (5),
(6)。
5. the preparation method as described in claim any one of 1-4, it is characterised in that in step (7), described graphitization processing
Method and condition can be the method and condition of this area ordinary graphiteization processing, and the temperature of described graphitization processing is preferably
2800~3000 DEG C.
A kind of 6. natural micro crystal graphite negative material of modification, it is characterised in that the D of the material50For 9~21 μm.
7. negative material as claimed in claim 6, it is characterised in that the natural micro crystal graphite negative material of the modification has
Core shell structure, the core are the native graphite that Delanium is filled with hole, and the shell is Delanium；
Preferably, in the natural micro crystal graphite hole Delanium filling rate >=98%；
Preferably, the D of the negative material50For 9~21 μm；
Preferably, the mass fraction that Delanium accounts for negative material in the negative material is 7~10%, more preferably 8%；
Preferably, the tap density of the negative material is 1.1~1.25g/cm3。
8. the purposes of negative material as claimed in claims 6 or 7, it is used for the negative pole for preparing lithium-ion-power cell.
9. a kind of negative pole of lithium-ion-power cell, it includes the natural micro crystal graphite of modification as claimed in claims 6 or 7 and born
Pole material.
10. a kind of lithium-ion-power cell, it includes the negative pole of lithium-ion-power cell as claimed in claim 9.
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