CN103855395B - A kind of natural graphite cathode material of lithium ion battery and preparation method thereof - Google Patents
A kind of natural graphite cathode material of lithium ion battery and preparation method thereof Download PDFInfo
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- 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
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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Abstract
The invention discloses a kind of preparation method of natural graphite cathode material of lithium ion battery and its obtained natural graphite cathode material of lithium ion battery, this its comprise the steps：1. under 500 ~ 600 DEG C of temperature conditionss, spherical natural graphite is subjected to high temperature pretreatment, the time of processing is 4 ~ 6 hours；2. by step 1. in spherical natural graphite, graphitization catalyst and asphalt are well mixed to obtain compound；3. by step 2. in compound charing process, catalyzed graphitization high-temperature process is carried out after cooling again；4. it is classified, you can.The preparation method simple possible of the graphite cathode material of the present invention, it is adaptable to industrialized production.The discharge capacity of the graphite cathode material of the present invention is big, good cycle, the high comprehensive performance of its button cell being made.
Description
Technical field
The present invention relates to a kind of natural graphite cathode material of lithium ion battery and preparation method thereof.
Background technology
Miniaturization and universalness with electronic installation, have increasing need for the secondary cell of more Large Copacity.Especially make us looking steadily
Purpose is lithium ion battery, compared with NI-G or Ni-MH battery, has higher energy density using lithium ion battery.Although mesh
It is preceding for improve battery capacity carried out it is widely studied, still, with the raising to battery performance requirements, it is necessary to further
Improve battery capacity.
Native graphite has very high capacitance (＞ 350mAh/g), but there is structural unstable shortcoming.When in order to
When obtaining higher electrode density and improving squeeze pressure, graphite cathode particle is easy to abreast be orientated with collector, whole
Consistent orientation is produced on electrode, due to there is insertion lithium in graphite, so obtained electrode is easy to expansion.Electrode expansion makes electricity
Pond active material in unit volume can loading reduction, produce battery capacity the problem of reduce.
United States Patent (USP) US2006001003 reports the method that catalyzed graphitization handles Delanium class negative material, can change
Kind fast charging and discharging performance and cycle performance, but this method causes graphite negative electrodes material to be put into tap density reduction, compares surface
Product becomes big.Japan Patent JP2000-182617 mixes the high crystalline graphite such as flake natural graphite with pitch, size-reduced,
Charing, graphitization and compound is made, the deficiency of native graphite can be improved, i.e. first charge-discharge efficiency is high, cycle characteristics is excellent
Different, capacity is big and coating is excellent；But size-reduced, charing, graphitization and compound is made, the mixing of pitch amount it is excessive or not
Uniformly, capacity of material etc. is influenced whether.
The content of the invention
The technical problems to be solved by the invention are to overcome existing graphite cathode material discharge capacity low, cycle performance
There is provided a kind of natural graphite cathode material of lithium ion battery and preparation method thereof for the defect of difference.The preparation method letter of the present invention
Single feasible, it is adaptable to which that industrialized production, obtained natural graphite negative electrode material chemical property is good, reversible lithium storage capacity is big,
With high charge-discharge capacity and efficiency for charge-discharge, high rate during charging-discharging is good, and cycle performance is good, only has during charging small swollen
Swollen, security is good, preferable to electrolyte and other additive adaptability, and using obtained by the natural graphite negative electrode material
Lithium ion battery product property is stable, almost without difference between batch.
The present invention solves above-mentioned technical problem by the following technical programs.
One of technical scheme has been to provide a kind of preparation side of natural graphite cathode material of lithium ion battery
Method, it comprises the steps：
1. spherical natural graphite is carried out into high temperature at a temperature of 500 ~ 600 DEG C to pre-process 4 ~ 6 hours；
2. at a temperature of 100 ~ 180 DEG C, by step 1. in spherical natural graphite, with graphitization catalyst and asphalt
Stirring 1-1.5 hours is mediated, compound is well mixed to obtain；
3. by step 2. in compound charing process, catalyzed graphitization high-temperature process is carried out after cooling again；
4. it is classified, you can.
Step 1. in, described spherical natural graphite can select the conventional spherical natural graphite in this area；Described is spherical
The particle diameter of native graphite can be the conventional particle size of the such material in this area；Preferably, the volume of described spherical natural graphite is put down
Equal particle diameter D50 is 12 ~ 36 μm.
Step 2. in, described graphitization catalyst can select the conventional graphitization catalyst in this area；Preferably, described
Graphitization catalyst be silicon carbide, more preferably SiC；Preferably, the consumption of described graphitization catalyst is spherical
The 4 ~ 9% of the 2 ~ 12% of native graphite gross mass, more preferably spherical natural graphite gross mass, the percentage is natural to account for ball-type
The mass percent of graphite.
Step 2. in, the method and condition of described mixing are the conventional method and condition in this area, preferably, described
Mixing is carried out using cantilever double-spiral conical mixer, more preferably, and the time of described mixing is 2.0 ~ 3.5 hours.
Step 2. in, described asphalt can select the asphalt of this area all size；Preferably, described stone
Oil asphalt is middle fire stons oil asphalt；
Wherein, aromatic compound and oxygen-containing, nitrogenous, sulfur heterocyclic compound of the described mid temperature pitch more than three rings
And a small amount of macromolecule carbon material composition, molecular weight ranges 200~2000,3000 are reached as high as, softening point is 65~90 DEG C.
The consumption of described asphalt is the conventional consumption in this area；Preferably, described compound and asphalt
Mass ratio be（2:1）~（6:1）, more preferably（3:1）~（4:1）.
Step 3. in, the method and condition of described charing process are the conventional method and condition in this area；Preferably, institute
The temperature for the charing process stated is 800 ~ 1500 DEG C；The time of described charing process is 2 ~ 6 hours.By common sense in the field, institute
The charing process stated is carried out in an inert atmosphere, preferably, described inert gas is nitrogen.
Step 3. in, the method and condition of described cooling are the conventional method and condition in this area, are preferably cooled down
To room temperature.In the present invention, described room temperature is the conventional ambient temperature in this area, preferably 5 ~ 30 DEG C, more preferably 25 DEG C ~
26℃。
Step 3. in, the method and condition of described catalyzed graphitization high-temperature process are the conventional method in this area and bar
Part；Preferably, the temperature of described catalyzed graphitization high-temperature process is 2800 ~ 3200 DEG C；At described catalyzed graphitization high temperature
The time of reason is 24 ~ 48 hours.By common sense in the field, described catalyzed graphitization high-temperature process is carried out in an inert atmosphere, compared with
Good, described inert gas is nitrogen.
Step 4. in, the method and condition of described classification are the conventional method and condition in this area；It is preferably advanced
Row screening carries out Hydrodynamic Fractionation again, wherein, described screening and the method for Hydrodynamic Fractionation and condition are that this area is normal
The method and condition of rule；Preferably, described is sieving through 250 mesh sieve extracting screen underflows, more preferably, sieved using 250 mesh oscillatory types
Machine is carried out；Preferably, described Hydrodynamic Fractionation is carried out using gas flow sizing machine；More preferably, described gas flow sizing machine
Frequency is 25 ~ 65Hz.After described classification, the volume average particle size D50 of described graphite cathode material is 10 ~ 30 μm.
The two of technical scheme are to provide a kind of lithium ion battery native graphite as made from above-mentioned preparation method
Negative material.
Wherein, the volume average particle size D50 of described natural graphite cathode material of lithium ion battery is 10 ~ 36 μm.It is described
Graphite cathode material specific surface area be 3.0 ~ 4.0m2/g.The real density of described graphite cathode material is in 2.20g/cm3With
On, no more than 2.26g/cm3.The ash content of described graphite cathode material is in below 0.10wt%.
On the basis of common sense in the field is met, above-mentioned each optimum condition can be combined, and produce each preferable reality of the present invention
Example.
Agents useful for same and raw material of the present invention are commercially available.
The positive effect of the present invention is：
1st, the discharge capacity of graphite cathode material of the invention is big, good cycle, the synthesis of its button cell being made
Function admirable, mainly has the advantage that：1）Chemical property is good, and discharge capacity is in more than 350mAh/g；2）Discharge platform and flat
Platform conservation rate is higher；3）High rate during charging-discharging is preferable；4）Good cycle（300 circulations, capacity keeps >=80%）；5）
Security is preferable（It is 130 DEG C/60 minutes, not quick-fried, do not rise）；6）It is preferable to electrolyte and other additive adaptability；7）It is made
Product property it is stable, almost without difference between batch.
2nd, the preparation method simple possible of graphite cathode material of the invention, it is adaptable to industrialized production.
Brief description of the drawings
Fig. 1 is the first charge-discharge curve of the natural graphite negative electrode material of the embodiment of the present invention 2.
Fig. 2 is the imbibition linearity curve of the natural graphite negative electrode material of the embodiment of the present invention 2.
Fig. 3 is the cycle performance figure of the natural graphite negative electrode material of the embodiment of the present invention 2.
Embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to described reality
Apply among a scope.The experimental method of unreceipted actual conditions in the following example, conventionally and condition, or according to business
Product specification is selected.
In the present invention, described raw material and its manufacturer and model see the table below：
The manufacturer of each raw material of table 1 and model
| Raw material | Manufacturer and model |
| Native graphite | Shanghai Shanshan Science and Technology Co., Ltd's spherical natural graphite |
| SiC | Linyi Jinmeng Silicon Carbide Co., Ltd.'s NAT6 carborundum |
| Asphalt | The bright reinforcing work Materials Co., Ltd MQ-100 mid temperature pitches in Dalian |
| Coal tar pitch | Henan Bo Hai Chemical Co., Ltd.s mid temperature pitch |
Embodiment 1
1. by pretreatments of the volume average particle size D50 for 19.3 μm of 500 DEG C of native graphite 20kg progress, processing time is
4 hours；2. by the volume average particle size D50 after processing for 19.3 μm native graphite 20kg and graphitization catalyst（SiC）
0.8kg is added in cantilever double helix conical agitator and mixed 2 hours, obtains compound；Stirring it is lower alternately by compound 20.8kg and
Asphalt 4kg is added in kneading pot, carries out mediating stir process 1.5 hours in 100 DEG C；3. under the protection of nitrogen,
Charing process 2 hours at a temperature of 1100 DEG C, are cooled to 5 DEG C of room temperature by reaction product afterwards, are carried out 36 hours then at 2800 DEG C
Catalyzed graphitization high-temperature process；4. sieved using 250 mesh oscillatory type screening machines, screenings is classified using gas flow sizing machine,
The frequency of grading wheel is 48Hz, obtains the graphite negative material of lithium ion battery that particle volume average grain diameter D50 is 20.6 μm.Measure
Its half-cell capacity is 362.5mAh/g, first charge-discharge efficiency 91.1%.
Embodiment 2
1. by pretreatments of the volume average particle size D50 for 17.8 μm of 600 DEG C of native graphite 20kg progress, processing time is
5 hours；2. it is 17.8 μm of native graphite 20kg graphitization catalysts by the volume average particle size D50 after processing（SiC）0.8kg
Add in cantilever double helix conical agitator and mix 2 hours, obtain compound；Stirring is lower alternately by compound 20kg and asphalt
3kg is added in kneading pot, carries out mediating processing 1 hour in 160 DEG C；3. under the protection of nitrogen, and at a temperature of 800 DEG C
Charing process 6 hours, is cooled to 30 DEG C of room temperature by reaction product afterwards, then at 3000 DEG C of progress, 48 hours catalyzed graphitization high temperature
Processing；5. sieved using 250 mesh oscillatory type screening machines, screenings is classified using gas flow sizing machine, and the frequency of grading wheel is
35Hz, obtains the graphite negative material of lithium ion battery that particle volume average grain diameter D50 is 18.4 μm.Measure its half-cell capacity
363.5mAh/g, first charge-discharge efficiency 92.4%.
Embodiment 3
1. by pretreatments of the volume average particle size D50 for 12.1 μm of 500 DEG C of native graphite 20kg progress, processing time is
4 hours；2. by the volume average particle size D50 after processing for 12.1 μm native graphite 20kg and graphitization catalyst（SiC）
1.2kg is added in cantilever double helix conical agitator and mixed 3 hours, obtains compound；Stirring it is lower alternately by compound 21.2kg and
Asphalt 4kg is added in kneading pot, carries out mediating processing 1.5 hours in 100 DEG C；3. under the protection of nitrogen, and
Charing process 3 hours at a temperature of 1500 DEG C, are cooled to 26 DEG C of room temperature by reaction product afterwards, are carried out 48 hours then at 3200 DEG C
Catalyzed graphitization high-temperature process；4. sieved using 250 mesh oscillatory type screening machines, screenings is classified using gas flow sizing machine,
The frequency of grading wheel is 45Hz, obtains the graphite negative material of lithium ion battery that particle volume average grain diameter D50 is 13.2 μm.Measure
Its half-cell capacity 365.2mAh/g, first charge-discharge efficiency 93.5%.
Embodiment 4
1. by pretreatments of the volume average particle size D50 for 35.8 μm of 500 DEG C of native graphite 20kg progress, processing time is
4 hours；2. by volume average particle size D50 for 35.8 μm native graphite 20kg and graphitization catalyst（SiC）1.8kg adds outstanding
Mixed 3.5 hours in arm double helix conical agitator, obtain compound；Stirring is lower alternately by compound 21.8kg and asphalt
8kg is added in kneading pot, carries out mediating processing 1 hour in 180 DEG C；3. under the protection of nitrogen, and in 1100 DEG C of temperature
Lower charing process 2 hours, is cooled to 24 DEG C of room temperature by reaction product afterwards, then at 3200 DEG C of progress, 24 hours catalyzed graphitization height
Temperature processing；4. sieved using 250 mesh oscillatory type screening machines, screenings is classified using gas flow sizing machine, the frequency of grading wheel
For 20Hz, the graphite negative material of lithium ion battery that particle volume average grain diameter D50 is 36.2 μm is made.Measure its half-cell appearance
Measure 366.3mAh/g, first charge-discharge efficiency 92.1%.
Embodiment 5
1. by pretreatments of the volume average particle size D50 for 17.8 μm of 600 DEG C of native graphite 20kg progress, processing time is
5 hours；2. it is 17.8 μm of native graphite 20kg graphitization catalysts by the volume average particle size D50 after processing（SiC）0.4kg
Add in cantilever double helix conical agitator and mix 2 hours, obtain compound；Stirring is lower alternately by compound 20kg and asphalt
3kg is added in kneading pot, carries out mediating processing 1 hour in 160 DEG C；3. under the protection of nitrogen, and at a temperature of 800 DEG C
Charing process 6 hours, is cooled to 25 DEG C of room temperature by reaction product afterwards, then at 3000 DEG C of progress, 48 hours catalyzed graphitization high temperature
Processing；5. sieved using 250 mesh oscillatory type screening machines, screenings is classified using gas flow sizing machine, and the frequency of grading wheel is
35Hz, obtains the graphite negative material of lithium ion battery that particle volume average grain diameter D50 is 18.5 μm.Measure its half-cell capacity
365.3mAh/g, first charge-discharge efficiency 92.4%.
Embodiment 6
1. by pretreatments of the volume average particle size D50 for 35.8 μm of 500 DEG C of native graphite 20kg progress, processing time is
4 hours；2. by volume average particle size D50 for 35.8 μm native graphite 20kg and graphitization catalyst（SiC）2.4kg adds outstanding
Mixed 3.5 hours in arm double helix conical agitator, obtain compound；Stirring is lower alternately by compound 21.8kg and asphalt
8kg is added in kneading pot, carries out mediating processing 1 hour in 180 DEG C；3. under the protection of nitrogen, and in 1100 DEG C of temperature
Lower charing process 2 hours, is cooled to 26 DEG C of room temperature by reaction product afterwards, then at 3200 DEG C of progress, 24 hours catalyzed graphitization height
Temperature processing；4. sieved using 250 mesh oscillatory type screening machines, screenings is classified using gas flow sizing machine, the frequency of grading wheel
For 20Hz, the graphite negative material of lithium ion battery that particle volume average grain diameter D50 is 36.4 μm is made.Measure its half-cell appearance
Measure 366.2mAh/g, first charge-discharge efficiency 92.6%.
Comparative example 1
Native graphite is without high temperature pre-treatment step in the embodiment.
Volume average particle size D50 high temperature pretreatment is not done into for 19.3 μm of native graphite, directly with 14kg and graphitization
Catalyst（SiC）1.2kg is added in cantilever double helix conical agitator and mixed 2 hours, obtains compound；Stirring is lower alternately will mixing
Material 20kg and asphalt 8kg is added in reactor, carries out hot cladding processing, cladding terminate after at a temperature of 1100 DEG C charcoal
Change processing 2 hours, reaction product is cooled to 27 DEG C of room temperature afterwards, carried out then at 3200 DEG C at 48 hours catalyzed graphitization high temperature
Reason, is sieved using 250 mesh oscillatory type screening machines, and the silicon/carbon/graphite in lithium ion batteries that particle volume average grain diameter D50 is 19.3 μm is made
Negative material.Measure its half-cell capacity 360.4mAh/g, first charge-discharge efficiency 87.7%.
Comparative example 2
Native graphite does not do catalyzed graphitization high-temperature process in the embodiment.
14kg volume average particle sizes D50 is pre-processed 4 hours for 19.3 μm native graphite 600 DEG C of high temperature of progress；Again will
14kg native graphites after processing, which are added in cantilever double helix conical agitator, to be mixed 2 hours, obtains graphite raw material；Stirring is lower to hand over
It is added to for by composite graphite raw material 20kg and asphalt 8kg in kneading pot, carries out mediating processing 1 hour in 160 DEG C, mediate
After end, under the protection of nitrogen, and charing process 2 hours at a temperature of 1100 DEG C, reaction product is cooled to room afterwards
26 DEG C of temperature；Sieved using 250 mesh oscillatory type screening machines, screenings is classified using gas flow sizing machine, and the frequency of grading wheel is
48Hz, is made the graphite negative material of lithium ion battery that particle volume average grain diameter D50 is 19.1 μm.Measure its half-cell capacity
344.3mAh/g, first charge-discharge efficiency 90.2%.
Comparative example 3
Binding agent is coal tar pitch in the embodiment.
14kg volume average particle sizes D50 is pre-processed 4 hours for 24.6 μm native graphite 600 DEG C of high temperature of progress, then will
Native graphite 20kgs and graphitization catalyst of the volume average particle size D50 for 24.6 μm after processing（SiC）1.2kg adds cantilever
Mixed 2 hours in double helix conical agitator, obtain graphite raw material；Stirring is lower alternately by graphite raw material 21.2kg and coal tar pitch
5kg is added in kneading pot, carries out mediating processing 1 hour in 180 DEG C, after kneading terminates, under the protection of nitrogen, and 1100
Charing process 2 hours at a temperature of DEG C, are cooled to 25 DEG C of room temperature by reaction product afterwards, carry out being catalyzed for 48 hours then at 3200 DEG C
Graphitizable high temperature processing；Sieved using 250 mesh oscillatory type screening machines, screenings is classified using gas flow sizing machine, grading wheel
Frequency be 45Hz, the graphite negative material of lithium ion battery that particle volume average grain diameter D50 is 25.4 μm is made.Measure it partly
Battery capacity 365.3mAh/g, first charge-discharge efficiency 86.7%.
Effect example 1
（1）Carry out particle diameter, real density respectively to the graphite cathode material in embodiment 1 ~ 4 and comparative example 1 ~ 3, compare surface
Product and grey grade an index test and discharge capacity, the test of first charge-discharge efficiency, the results are shown in Table 2.
Instrument title and model used in test：
Volume average particle size D50, laser fineness gage MS2000；
Real density, super constant temperature water tank SC-15；
Ash content, high-temperature electric resistance furnace SX2-2.5-12；
Specific surface area, specific surface area measuring instrument NOVA2000.
Assay method national standard：
Tap density GB/T5162-2006/ISO3953:1993；
Real density GBT 8330-2008；
Specific surface area GB/T 19587-2004.
Half-cell method of testing is：Composite graphite negative electrode material, the 1-METHYLPYRROLIDONE containing 6 ~ 7% Kynoar
And 2% conductive black in mass ratio 91.6:6.6:1.8 ratio is well mixed, and is applied on copper foil, the pole piece coated is put into
Temperature is standby to be dried in vacuo 4 hours in 110 DEG C of vacuum drying chambers.Simulated battery is assemblied in the German Braun gloves of applying argon gas
Carried out in case, electrolyte is 1MLiPF6+EC:DEC:DMC=1:1:1（Volume ratio）, metal lithium sheet is to electrode, electrochemistry
It can test and be carried out on U.S. ArbinBT2000 type cell testers, charging/discharging voltage scope is 0.005 to 1.0V, discharge and recharge
Speed is 0.1C.
The performance parameter of the graphite cathode material of each embodiment of table 2 and comparative example
From table 2 it can be seen that the discharge capacity of each sample of embodiment 1 ~ 6 is all in more than 360mAh/g, and fill first
Discharging efficiency is all more than 91%.
Comparative example 1 is that native graphite does not do high-temperature process, each first charge-discharge efficiency of embodiment 1 ~ 4 more than 91%,
And the first charge-discharge efficiency of comparative example 1 only has 87.7%, first charge-discharge efficiency is relatively low.
Comparative example 2 is that native graphite does not do catalyzed graphitization high-temperature process, and each discharge capacity of embodiment 1 ~ 4 exists
More than 362mAh/g, and the discharge capacity of comparative example 1 only has 344.3mAh/g, discharge capacity is low.
The binding agent of comparative example 3 is coal tar pitch, and the binding agent of embodiment 1 ~ 6 is asphalt, and its first charge-discharge efficiency exists
More than 91%, and the first charge-discharge efficiency of comparative example 3 only has 86.7%, first charge-discharge efficiency is relatively low.
It can be seen that, the graphite negative material of lithium ion battery prepared using preparation method of the present invention, specific surface area is controlled 3.0
~4.0m2/ g, both can guarantee that particle surface pore was flourishing, be conducive to suppressing lithium-ion battery system generation ballooning, battery again
Have a safety feature；Discharge capacity is up to more than 360mAh/g；The loss of irreversible capacity is reduced, energy density is improved,
Reduce the consumption of positive pole；Pole piece processability is good, high compacted density 1.70g/cm3Under the imbibition time be less than 180 seconds.
（2）The graphite cathode material of embodiment 2 is tested using full battery testing method.Full battery testing method
For：Using composite graphite negative electrode material as negative pole, using cobalt acid lithium as positive pole, 1M-LiPF6EC:DMC:EMC=1:1:1（Volume
Than）Solution makees electrolyte assembling and helps battery, carries out electric performance test.
As a result show, sample has preferable voltage platform, discharge voltage can reach plateau quickly, as shown in Figure 1；
Its absorbent is excellent, high compacted density 1.70g/cm3Under the imbibition time be less than 180 seconds, as shown in Figure 2；Its cycle performance
Good, capability retention can reach 86.1% after circulating 300 times, as shown in Figure 3.
（3）The other continuous item range estimations of resultant battery that graphite negative material of lithium ion battery by embodiment 1 ~ 6 is made
Test result is：Discharge platform（3.6V）>=75%, 100 weeks platforms of circulation keep >=95%；Multiplying power discharging 3C capacity >=50%；300 times
Circulation, capability retention >=80%；Overcharge, high temperature short circuit, the security performance measuring stability such as thermal shock it is good, it is not on fire, it is not quick-fried
Fried, surface temperature is no more than 150 DEG C；To electrolyte and other additive adaptability preferably, lithium is not analysed；Product is stable, batch it
Between almost without difference.
Claims (23)
1. a kind of preparation method of natural graphite cathode material of lithium ion battery, it is characterised in that：It comprises the steps：
1. spherical natural graphite is carried out into high temperature at a temperature of 500~600 DEG C to pre-process 4~6 hours；
2. at a temperature of 100~180 DEG C, by step 1. in spherical natural graphite, pinch with graphitization catalyst and asphalt
Stirring 1-1.5 hours is closed, compound is well mixed to obtain；
3. by step 2. in compound charing process, catalyzed graphitization high-temperature process is carried out after cooling again；
4. it is classified, you can.
2. preparation method as claimed in claim 1, it is characterised in that：The volume average particle size of described spherical natural graphite
D50 is 12~36 μm.
3. preparation method as claimed in claim 1, it is characterised in that：Described graphitization catalyst is the carbide of silicon.
4. preparation method as claimed in claim 3, it is characterised in that：Described graphitization catalyst is SiC.
5. preparation method as claimed in claim 1, it is characterised in that：The consumption of described graphitization catalyst is spherical natural
The 2~12% of graphite gross mass, the percentage is the mass percent for accounting for spherical natural graphite.
6. preparation method as claimed in claim 5, it is characterised in that：The consumption of described graphitization catalyst is spherical natural
The 4~9% of graphite gross mass, the percentage is the mass percent for accounting for spherical natural graphite.
7. preparation method as claimed in claim 1, it is characterised in that：Step 2. in, described mixing uses cantilever double helix
Cone-type mixer is carried out.
8. preparation method as claimed in claim 1, it is characterised in that：Step 2. in, time of described mixing for 2.0~
3.5 hour.
9. preparation method as claimed in claim 1, it is characterised in that：Step 2. in, described asphalt is middle fire stons oil
Pitch.
10. preparation method as claimed in claim 1, it is characterised in that：Step 2. in, described compound and asphalt
Mass ratio is (2:1)~(6:1).
11. preparation method as claimed in claim 10, it is characterised in that：Step 2. in, described compound and asphalt
Mass ratio be (3:1)~(4:1).
12. preparation method as claimed in claim 1, it is characterised in that：Step 3. in, the temperature of described charing process is
800~1500 DEG C；The time of described charing process is 2~6 hours；Described charing process is carried out in an inert atmosphere；
Step 3. in, it is described to be cooled to be cooled to 5~30 DEG C；
Step 3. in, the temperature of described catalyzed graphitization high-temperature process is 2800~3200 DEG C；Described catalyzed graphitization is high
The time of temperature processing is 24~48 hours；Described catalytic graphite high-temperature process is carried out in an inert atmosphere.
13. preparation method as claimed in claim 12, it is characterised in that：Step 3. in, described charing process is in nitrogen gas
Carried out in atmosphere.
14. preparation method as claimed in claim 12, it is characterised in that：Step 3. in, it is described to be cooled to be cooled to 25 DEG C
~26 DEG C.
15. preparation method as claimed in claim 12, it is characterised in that：Step 3. in, described catalytic graphite high-temperature process
Carried out in nitrogen atmosphere.
16. preparation method as claimed in claim 1, it is characterised in that：Step 4. in, described classification first to be sieved
Hydrodynamic Fractionation is carried out again.
17. preparation method as claimed in claim 16, it is characterised in that：Described is sieving through 250 mesh sieve extracting screen underflows；It is described
Hydrodynamic Fractionation using gas flow sizing machine carry out；After described classification, the volume of described graphite cathode material is averaged
Particle diameter D50 is 10~30 μm.
18. preparation method as claimed in claim 17, it is characterised in that：Described screening uses 250 mesh oscillatory type screening machines
Carry out.
19. preparation method as claimed in claim 17, it is characterised in that：The frequency of described gas flow sizing machine be 25~
65Hz。
20. lithium ion battery native graphite made from a kind of preparation method as any one of claim 1,3~16 is born
Pole material.
21. natural graphite cathode material of lithium ion battery as claimed in claim 20, it is characterised in that：Its volume average particle size
D50 is 10~36 μm, and specific surface area is 3.0~4.0m2/ g, real density is in 2.20g/cm3More than, no more than 2.26g/cm3, ash
Divide in below 0.10wt%.
22. natural graphite cathode material of lithium ion battery made from a kind of preparation method as claimed in claim 2.
23. lithium ion battery natural graphite cathode made from a kind of preparation method as any one of claim 17~19
Material.
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| CN105024075A (en) * | 2014-12-18 | 2015-11-04 | 上海杉杉科技有限公司 | Negative electrode material for quickly rechargeable graphite lithium-ion battery and preparation method of negative electrode material |
| CN105304870B (en) * | 2015-09-22 | 2018-01-02 | 江西正拓新能源科技有限公司 | Secondary granulation lithium ion battery negative material and preparation method thereof |
| CN106505198A (en) * | 2015-09-25 | 2017-03-15 | 宁波杉杉新材料科技有限公司 | A kind of graphite negative material of lithium ion battery and preparation method thereof |
| CN107871854A (en) * | 2016-09-27 | 2018-04-03 | 宁波杉杉新材料科技有限公司 | A kind of preparation method of graphite negative material of lithium ion battery second particle |
| CN110828824B (en) * | 2019-11-26 | 2021-06-11 | 湖南中科星城石墨有限公司 | Long-life natural graphite negative electrode material and preparation method thereof |
| CN114914408B (en) * | 2021-02-10 | 2024-06-11 | 中国石油化工股份有限公司 | Silicon-carbon composite material and preparation method and application thereof |
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