CN103794765B - A kind of graphite negative material of lithium ion battery and preparation method thereof - Google Patents
A kind of graphite negative material of lithium ion battery and preparation method thereof Download PDFInfo
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- CN103794765B CN103794765B CN201210422893.XA CN201210422893A CN103794765B CN 103794765 B CN103794765 B CN 103794765B CN 201210422893 A CN201210422893 A CN 201210422893A CN 103794765 B CN103794765 B CN 103794765B
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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
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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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- 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 kind of graphite negative material of lithium ion battery and preparation method thereof.The preparation method of the graphite negative material of lithium ion battery comprises the steps：（1）The mixture for including native graphite and pitch is heated and mediated, is crushed；Wherein, the average grain diameter D50 of described native graphite is 5 ~ 10 μm, and the mass ratio of described native graphite and described pitch is 50:50~90:10；（2）Under inert gas shielding, it is heat-treated in 300 ~ 700 DEG C；（3）Graphitization, you can.The average grain diameter D50 of graphite negative material of lithium ion battery prepared by the present invention is between 10 ~ 25 μm, and specific surface area is in 2.0m2/ below g, discharge capacity is in more than 360mAh/g first for battery made of the graphite negative material of lithium ion battery, and first charge-discharge efficiency is more than 90%, discharge-rate（2C/0.2C）More than 90%, product discharge capacity and efficiency for charge-discharge are high, good rate capability.
Description
Technical field
The present invention relates to graphite cathode material field, more particularly to a kind of graphite negative material of lithium ion battery and its preparation
Method.
Background technology
Lithium ion battery compared with original battery, with its energy density it is high, have extended cycle life, memory-less effect the features such as,
Popularized rapidly in mobile phone, notebook computer and electric tool etc..As various products are to small-size light-weight and more work(
Energy, the requirement of drivingization is continuously increased for a long time, and product also increasingly improves to the capacity requirement of lithium ion battery, at present lithium ion
The raising of battery capacity depends on the development of negative material and perfect.Therefore, for a long time, negative electrode of lithium ion battery is improved
The specific capacity of material, irreversible capacity first is reduced, improve multiplying power property, be always the emphasis of research and development.
The native graphite that ion secondary battery cathode material lithium uses has preferable layer structure, and there is very high electric discharge to hold
Amount（Close to theoretical capacity 372mAh/g）, cost is low but it has structural instability, easily causes the common insertion of solvent molecule, makes it
Synusia comes off in charge and discharge process, causes cycle performance of battery poor, security is poor.
Therefore, to overcome the shortcomings of native graphite performance, prior art is all that processing is modified to native graphite.Japan
Patent JP10294111 carries out low temperature cladding to graphite Carbon Materials with pitch, must not melted processing and slight powder after cladding
Broken, this method, which is difficult to, to be evenly coated.Japan Patent JP11246209 is in 10~300 DEG C of temperature by graphite and hard charcoal particle
Impregnated under degree in pitch or tar, then carry out solvent separation and heat treatment, this method are difficult in graphite and hard charcoal surface
The bitumen layer with certain thickness high polymeric is formed, the raising for native graphite structural stability is limited.Day
This patent JP2000003708 mechanically carries out rounding to graphite material, is then carried out in heavy oil, tar or pitch
Dipping, then separated and washed, it is close with JP 11246209 in terms of method for coating merely.Japan Patent JP2000182617
It is that can reduce graphite material with pitch or resin or its mixture Co carbonization, this method using native graphite etc. and compare surface
Product, but be difficult on covered effect to reach preferable control.Japan Patent JP2000243398 is to utilize gas caused by asphalt pyrolysis
Atmosphere is surface-treated to graphite material, and this method is unlikely, and make the to be modified form of material is greatly improved, thus
It is restricted the raising of electrical property.Japan Patent JP2002042816 is using aromatic hydrocarbons as raw material chemical vapor deposition（CVD）Method
Coated or coated with pitch phenolic resin, this has similar to JP2000182617 and JP2000283398 in effect
Part.
The content of the invention
Technical problem solved by the invention is to overcome the graphite cathode material stability of existing asphalt modification
Difference, the defects of battery capacity is not high, there is provided a kind of graphite negative material of lithium ion battery and preparation method thereof.The system of the present invention
Preparation Method yield is high, and process is simple, obtained product graphite negative material of lithium ion battery multiplying power while high power capacity is obtained
Performance is also improved.
The present invention is that solve above-mentioned technical problem by the following technical programs.
The invention provides a kind of preparation method of graphite negative material of lithium ion battery, it comprises the steps：
（1）The mixture for including native graphite and pitch is heated and mediated, is crushed；Wherein, described native graphite
Average grain diameter D50 is 5 ~ 10 μm, and the mass ratio of described native graphite and described pitch is 50:50~90:10；
（2）Under inert gas shielding, it is heat-treated in 300 ~ 700 DEG C；
（3）Graphitization, you can.
Step（1）In, described native graphite is preferably potato shape and/or spherical.Described native graphite is averaged
Particle diameter D50 is preferably 6 ~ 8 μm.
Step（1）In, described pitch can be this area in conventional use of pitch, the present invention in, described pitch compared with
It is good for asphalt and/or coal tar pitch.The average grain diameter D50 of described pitch is preferably 2 ~ 10 μm.
Step（1）In, the mass ratio of described native graphite and described pitch is preferably 60:40~80:20.
Step（1）In, described mixture can also include graphitization catalyst commonly used in the art, described stone
Inkization catalyst is preferably the carbide of silicon and/or the oxide of iron, more preferably carborundum and/or iron oxide.Described
The mass ratio of graphitization catalyst and native graphite is preferably 1:50~7:90, more preferably 3:100~3:50.
Step（1）In, the hybrid mode of described mixture is preferably to be carried out using cantilever double-spiral conical mixer
Mixing, native graphite and pitch can be alternately added in charging, it is well mixed consistent to ensure；Wherein, described cantilever is double
The rotating speed of cone and screw mixer is preferably 35 ~ 37rpm；The time of described mixing is preferably 2 ~ 3 hours.Preferably,
After being mixed using cantilever double-spiral conical mixer, then mixed in kneading pot.
Described heating kneading processing can make graphite particle equably modified bonding, and its concrete operation method can use this
The conventional method in field is carried out, and by above-mentioned native graphite and the mixture heat temperature raising of pitch, carries out kneading processing, such as mixed
Pinch and kneading processing is carried out in pot.
Step（1）In, the temperature that described heating is mediated is preferably 100 ~ 180 DEG C.The time that described heating is mediated
Preferably 1 ~ 10 hour, heating kneading time it is short material can be caused to lump, mixing it is uneven, heating kneading time length can cause
Binder pitch volatilization loss, influences adhesive effect.
Step（1）In, described crushing is preferably to be crushed using mechanical beater disintegrating machine, and crushing is to ensure
Grain is bonded uniformly.
Step（2）In, described inert gas is preferably nitrogen and/or argon gas.
Step（2）In, the temperature of described heat treatment is preferably 400 ~ 600 DEG C.The time of described heat treatment is preferable
For 12 ~ 24 hours.
Step（3）In, described graphitizing method can be method for graphitizing commonly used in the art, in the present invention,
Graphited temperature is preferably 2400 ~ 2800 DEG C.The graphited time is preferably 20 ~ 60 hours.
In the present invention, sieve classification step can be also included after described graphitization step.
Wherein, the method for described sieve classification can be this area conventional method, preferably using oscillatory type screening machine
And/or ultrasonic type screening machine classification.Ensure that the average grain diameter D50 of particle reaches 10 ~ 25 μm by sieve classification, the shape of product
Looks, function can be more preferably.
Present invention also offers one kind graphite negative material of lithium ion battery as made from above-mentioned preparation method.
The graphite negative material of lithium ion battery obtained with above-mentioned preparation method, its average grain diameter D50 can 10 ~ 25 μm it
Between, specific surface area can be in 2.0m2/ below g, in of the invention, in button made of preferable graphite negative material of lithium ion battery
Performance test is carried out in battery, discharge capacity is in more than 360mAh/g first, and first charge-discharge efficiency is more than 90%, electric discharge times
Rate（2C/0.2C）More than 90%, product discharge capacity and efficiency for charge-discharge are high, good rate capability, its performance parameter such as institute of table 1
Show.
The performance parameter of the graphite negative material of lithium ion battery of table 1
As seen from the above table, graphite negative material of lithium ion battery of the invention significantly reduces specific surface area, improves
Discharge capacity and discharging efficiency, the high comprehensive performance of its manufactured button cell.
It on the basis of common sense in the field is met, above-mentioned each optimum condition, can be combined, it is each preferably real to produce 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：
（1）The preparation method simple process of the present invention is easy, and raw material sources are extensive and cost is low.
（2）The methods of graphite negative material of lithium ion battery of the present invention employs asphalt modification granulation processing, graphitization,
Obtained product discharge capacity and efficiency for charge-discharge are high, good rate capability.
Brief description of the drawings
Fig. 1 is the first charge-discharge curve of the graphite cathode material of the embodiment of the present invention 2.
Fig. 2 is the scanning electron microscope (SEM) photograph of the graphite cathode material of the embodiment of the present invention 2.
Fig. 3 is the high rate performance figure of the graphite cathode 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 selects.
Native graphite is the QDC-80 native graphites of Qingdao Tai Neng graphite Co., Ltd production.
Asphalt is the bright MQ-260 oil hard pitches for strengthening the production of work Materials Co., Ltd in Dalian.
Coal tar pitch is the modified coal tar pitch of Henan Bo Hai Chemical Co., Ltd.s production.
SiC is the GCF carborundum of Linyi Jin Meng carborundum Co., Ltd production.
Embodiment 1
By native graphite（D50 is 6.0 μm）16kg, asphalt（D50 is 4.0 μm）4kg and graphitization catalyst（SiC）
0.8kg is alternately added in cantilever double-spiral conical mixer and mixed 2 hours, is added in kneading pot and mixes under stirring, is heated to 160
DEG C carry out mediating processing 3 hours, after kneading terminates, sheet is pressed into tablet press machine, beater disintegrating machine crushes.In the guarantor of nitrogen
Under shield, and heat treatment granulation is carried out at 500 DEG C, heat treatment granulation time 12 hours, reaction product is cooled to room temperature afterwards,
Catalyzed graphitization processing in 48 hours is carried out then at 2400 DEG C, graphite negative material of lithium ion battery is made.Its button cell capacity
For 364.9mAh/g, efficiency is 91.8% first, discharge-rate（2C/0.2C）For 93.8%.
Embodiment 2
By native graphite（D50 is 6.0 μm）16kg, coal tar pitch（D50 is 6.4 μm）4kg and graphitization catalyst（SiC）
0.8kg is alternately added in cantilever double-spiral conical mixer and mixed 2 hours, is added in kneading pot and mixes under stirring, is heated to 160
DEG C carry out mediating processing 5 hours, after kneading terminates, sheet is pressed into tablet press machine, beater disintegrating machine crushes.In the guarantor of nitrogen
Under shield, and heat treatment granulation is carried out at 500 DEG C, heat treatment granulation time 18 hours, reaction product is cooled to room temperature afterwards,
Catalyzed graphitization processing in 48 hours is carried out then at 2400 DEG C, graphite negative material of lithium ion battery is made.Its button cell capacity
For 363.7mAh/g, efficiency is 90.8% first, discharge-rate（2C/0.2C）For 94.0%.
Embodiment 3
By native graphite（D50 is 5.0 μm）10kg, asphalt（D50 is 4.0 μm）10kg and graphitization catalyst
（SiC）0.5kg is alternately added in cantilever double-spiral conical mixer and mixed 2 hours, is added in kneading pot and mixes under stirring, heating
Carry out mediating processing 10 hours to 100 DEG C, after kneading terminates, sheet is pressed into tablet press machine, beater disintegrating machine crushes.In nitrogen
Under the protection of gas, and heat treatment granulation is carried out at 700 DEG C, heat treatment granulation time 18 hours, afterwards cooled down reaction product
To room temperature, catalyzed graphitization processing in 20 hours is carried out then at 2500 DEG C, graphite negative material of lithium ion battery is made.Its button electricity
Tankage is 360.2mAh/g, and efficiency is 91.3% first, discharge-rate（2C/0.2C）For 92.1%.
Embodiment 4
By native graphite（D50 is 7.5 μm）14kg, asphalt（D50 is 4.0 μm）6kg and graphitization catalyst
（Fe2O3）0.7kg is alternately added in cantilever double-spiral conical mixer and mixed 2 hours, is added in kneading pot and mixes under stirring, adds
Heat carries out mediating processing 5 hours to 140 DEG C, after kneading terminates, sheet is pressed into tablet press machine, beater disintegrating machine crushes.
Under the protection of nitrogen, and heat treatment granulation is carried out at 600 DEG C, heat treatment granulation time 15 hours is cold by reaction product afterwards
But to room temperature, catalyzed graphitization processing in 60 hours is carried out then at 2800 DEG C, graphite negative material of lithium ion battery is made.Its button
Battery capacity is 360.5mAh/g, and efficiency is 91.2% first, discharge-rate（2C/0.2C）For 93.2%.
Embodiment 5
By native graphite（D50 is 6.0 μm）14kg, asphalt（D50 is 2.1 μm）6kg and graphitization catalyst（SiC）
0.3kg is alternately added in cantilever double-spiral conical mixer and mixed 2 hours, is added in kneading pot and mixes under stirring, is heated to 180
DEG C carry out mediating processing 1 hour, after kneading terminates, sheet is pressed into tablet press machine, beater disintegrating machine crushes.In the guarantor of nitrogen
Under shield, and heat treatment granulation is carried out at 300 DEG C, heat treatment granulation time 24 hours, reaction product is cooled to room temperature afterwards,
Catalyzed graphitization processing in 48 hours is carried out then at 2400 DEG C, graphite negative material of lithium ion battery is made.Its button cell capacity
For 362.2mAh/g, efficiency is 91.8% first, discharge-rate（2C/0.2C）For 93.0%.
Embodiment 6
By native graphite（D50 is 10.0 μm）18kg, coal tar pitch（D50 is 6.4 μm）2kg and graphitization catalyst（SiC）
0.9kg is alternately added in cantilever double-spiral conical mixer and mixed 2 hours, is added in kneading pot and mixes under stirring, is heated to 160
DEG C carry out mediating processing 2 hours, after kneading terminates, sheet is pressed into tablet press machine, beater disintegrating machine crushes.In the guarantor of nitrogen
Under shield, and heat treatment granulation is carried out at 500 DEG C, heat treatment granulation time 20 hours, reaction product is cooled to room temperature afterwards,
Catalyzed graphitization processing in 48 hours is carried out then at 2600 DEG C, graphite negative material of lithium ion battery is made.Its button cell capacity
For 360.8mAh/g, efficiency is 90.5% first, discharge-rate（2C/0.2C）For 92.0%.
Embodiment 7
By native graphite（D50 is 6.0 μm）14kg, coal tar pitch（D50 is 9.9 μm）6kg and graphitization catalyst（SiC）
1.1kg is alternately added in cantilever double-spiral conical mixer and mixed 2 hours, is added in kneading pot and mixes under stirring, is heated to 160
DEG C carry out mediating processing 2 hours, after kneading terminates, sheet is pressed into tablet press machine, beater disintegrating machine crushes.In the guarantor of nitrogen
Under shield, and heat treatment granulation is carried out at 400 DEG C, heat treatment granulation time 24 hours, reaction product is cooled to room temperature afterwards,
Catalyzed graphitization processing in 40 hours is carried out then at 2400 DEG C, graphite negative material of lithium ion battery is made.Its button cell capacity
For 361.2mAh/g, efficiency is 91.0% first, discharge-rate（2C/0.2C）For 93.8%.
Embodiment 8
By native graphite（D50 is 6.0 μm）14kg, asphalt（D50 is 4.0 μm）6kg is alternately added cantilever double helix
Mixed 2 hours in cone-type mixer, be added in kneading pot and mix under stirring, be heated to 160 DEG C and carry out mediating processing 2 hours, pinch
After conjunction terminates, sheet is pressed into tablet press machine, beater disintegrating machine crushes.Under the protection of nitrogen, and heat is carried out at 500 DEG C
Processing is granulated, and heat treatment granulation time 18 hours, reaction product is cooled into room temperature afterwards, then at 2800 DEG C of progress, 48 hours stone
Blackization processing, is made graphite negative material of lithium ion battery.Its button cell capacity is 355.9mAh/g, and efficiency is first
90.5%, discharge-rate（2C/0.2C）For 90.7%.
Comparative example 1
By native graphite（D50 is 9.8 μm）14kg, graphitization catalyst（SiC）0.7kg is alternately added cantilever double helix cone
Mixed 2 hours in shape mixer.Under the protection of nitrogen, and it is heat-treated at 500 DEG C, heat treatment time 18 hours, it
Reaction product is cooled to room temperature afterwards, catalyzed graphitization processing in 48 hours is carried out then at 2400 DEG C, silicon/carbon/graphite in lithium ion batteries is made
Negative material.Its button cell capacity is 354.1mAh/g, and efficiency is 87.2% first, discharge-rate（2C/0.2C）For
70.8%。
Comparative example 2
By native graphite（D50 is 15.8 μm）14kg, coal tar pitch（D50 is 6.4 μm）6kg and graphitization catalyst（SiC）
0.3kg is alternately added in cantilever double-spiral conical mixer and mixed 2 hours, is added in kneading pot and mixes under stirring, is heated to 160
DEG C carry out mediating processing 2 hours, after kneading terminates, sheet is pressed into tablet press machine, beater disintegrating machine crushes.In the guarantor of nitrogen
Under shield, and heat treatment granulation is carried out at 500 DEG C, heat treatment granulation time 20 hours, reaction product is cooled to room temperature afterwards,
Catalyzed graphitization processing in 48 hours is carried out then at 2600 DEG C, graphite negative material of lithium ion battery is made.Its button cell capacity
For 364.7mAh/g, efficiency is 90.0% first, discharge-rate（2C/0.2C）For 82.4%.
Effect example
（1）Graphite cathode material in embodiment 1 ~ 8 and comparative example 1,2 is subjected to particle diameter, specific surface area respectively
Deng item index test, the results are shown in Table 2.Instrument title and model used in test：Particle diameter, laser fineness gage
MS2000；Specific surface area, specific surface area measuring instrument NOVA2000.
（2）The graphite cathode material in embodiment 1 ~ 8 and comparative example 1,2 is entered using button cell method of testing
The test of row discharge capacity and first efficiency, as a result it is listed in table 2.
Button cell method of testing is used in the present invention：In carboxymethyl cellulose（CMC）Conductive black is added in the aqueous solution,
Then graphite sample is added, is eventually adding butadiene-styrene rubber（SBR）, stir, slurry be uniformly coated in copper on coating machine
Pole piece is made on paper tinsel.The pole piece coated is put into temperature to be dried in vacuo 4 hours in 110 DEG C of vacuum drying chambers, pole piece is taken out and exists
Rolled on roll squeezer, it is standby.Simulated battery is assemblied in the German Braun glove box of applying argon gas and carried out, and electrolyte is
1MLiPF6EC:DEC:DMC=1:1:1（Volume ratio）, metal lithium sheet is to electrode.Volume test is in U.S.'s ArbinBT2000 types
Carried out on cell tester, charging/discharging voltage scope is 0.005 to 2.0V, charge-discharge velocity 0.1C.
Discharge-rate method of testing is used in the present invention：The graphite of the embodiment of the present invention or comparative example makees negative pole, cobalt acid lithium
Make positive pole, 1MLiPF6EC:DMC:EMC=1:1:1（Volume ratio）Solution makees electrolyte assembling and helps battery, test 1C ~ 3C electric discharges
Multiplying power.
The performance parameter of the embodiment of table 2 and comparative example
Discharge capacity in comparative example 1 is can be seen that from the data in table 2 and efficiency for charge-discharge is low, non-bituminous bag
The efficiency for charge-discharge for covering the native graphite that heating is mediated is only 87.2%, discharge-rate（2C/0.2C）Only reach 70.8%；Contrast is real
The average grain diameter D50 for applying the native graphite in example 2 is more than 10 μm, and heating kneading effect is bad, and specific surface area is bigger than normal, discharge-rate
It is low；The negative material prepared using patent methods described, specific surface area substantially reduces, less than 2.0m2/ g, discharge capacity are more than
360mAh/g, efficiency for charge-discharge are more than 90%, discharge-rate（2C/0.2C）More than 90%.
Claims (13)
1. a kind of preparation method of graphite negative material of lithium ion battery, it is characterised in that it is made up of following step：
(1) mixture for including native graphite and pitch is heated and mediated, crushed；Wherein, described native graphite is averaged
Particle diameter D50 is 5~10 μm, and the mass ratio of described native graphite and described pitch is 50:50~90:10；
(2) under inert gas shielding, heat treatment granulation is carried out in 400~600 DEG C；
(3) graphitization, you can；
In step (1), described pitch is asphalt and/or coal tar pitch, and the average grain diameter D50 of described pitch is 2~10 μ
m。
2. the preparation method of graphite negative material of lithium ion battery as claimed in claim 1, it is characterised in that in step (1),
Described native graphite is potato shape and/or spherical.
3. the preparation method of graphite negative material of lithium ion battery as claimed in claim 1, it is characterised in that in step (1),
The average grain diameter D50 of described native graphite is 6~8 μm.
4. the preparation method of graphite negative material of lithium ion battery as claimed in claim 1, it is characterised in that in step (1),
The mass ratio of described native graphite and described pitch is 60:40~80:20.
5. the preparation method of graphite negative material of lithium ion battery as claimed in claim 1, it is characterised in that in step (1),
Described mixture also includes graphitization catalyst.
6. the preparation method of graphite negative material of lithium ion battery as claimed in claim 5, it is characterised in that described graphite
Change catalyst as the carbide of silicon and/or the oxide of iron, the mass ratio of described graphitization catalyst and native graphite is 1:
50~7:90.
7. the preparation method of the graphite negative material of lithium ion battery as described in claim 5 or 6, it is characterised in that described
Graphitization catalyst is carborundum and/or iron oxide, and the mass ratio of described graphitization catalyst and native graphite is 3:100~
3:50。
8. the preparation method of graphite negative material of lithium ion battery as claimed in claim 1, it is characterised in that in step (1),
The hybrid mode of mixture is replaced native graphite with pitch to be mixed using cantilever double-spiral conical mixer, during charging
Add；The rotating speed of described cantilever double-spiral conical mixer is 35~37rpm；The time of described mixing is 2~3 hours.
9. the preparation method of graphite negative material of lithium ion battery as claimed in claim 1, it is characterised in that in step (1),
Described heating is mediated and carried out in kneading pot, and the temperature that described heating is mediated is 100~180 DEG C, and described heating is mediated
Time be 1~10 hour.
10. the preparation method of graphite negative material of lithium ion battery as claimed in claim 1, it is characterised in that step (2)
In, the time of described heat treatment is 12~24 hours.
11. the preparation method of graphite negative material of lithium ion battery as claimed in claim 1, it is characterised in that step (3)
In, described graphited temperature is 2400~2800 DEG C, and the described graphited time is 20~60 hours.
12. the preparation method of graphite negative material of lithium ion battery as claimed in claim 1, it is characterised in that described stone
Sieve classification step is also included after inkization step.
13. graphite negative material of lithium ion battery made from the preparation method as described in any one in claim 1~12.
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| CN107601490A (en) * | 2017-08-11 | 2018-01-19 | 天津爱敏特电池材料有限公司 | A kind of fast charge graphite cathode material and preparation method thereof |
| CN109103453A (en) * | 2018-08-17 | 2018-12-28 | 东莞市凯金新能源科技股份有限公司 | A kind of preparation method and its material of the graphite cathode material of catalyzed graphitization |
| CN111244398A (en) * | 2018-11-28 | 2020-06-05 | 上海杉杉科技有限公司 | Composite graphite negative electrode material, lithium ion battery, preparation method and application |
| CN110350178A (en) * | 2019-07-12 | 2019-10-18 | 漳州巨铭石墨材料有限公司 | A kind of preparation method of lithium ion battery composite graphite negative electrode material |
| CN110723729B (en) * | 2019-09-26 | 2021-08-17 | 湖南中科星城石墨有限公司 | Kish graphite cathode material for lithium ion battery and modification process of Kish graphite cathode material |
| CN112542578B (en) * | 2020-12-24 | 2023-09-22 | 大连宏光锂业有限责任公司 | Composite graphite negative electrode material of lithium ion battery and preparation method thereof |
| CN112713271B (en) * | 2020-12-29 | 2022-07-05 | 上海杉杉科技有限公司 | Modified graphite material, preparation method thereof, lithium ion battery and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1547278A (en) * | 2003-12-12 | 2004-11-17 | 天津大学 | Putamen type carbon cathode material for lithium ion secondary battery and preparation method thereof |
| CN101053098A (en) * | 2004-08-30 | 2007-10-10 | 三菱化学株式会社 | Negative electrode material for nonaqueous secondary cells, negative electrode for nonaqueous secondary cells, and nonaqueous secondary cell |
| CN102593434A (en) * | 2011-01-11 | 2012-07-18 | 上海杉杉科技有限公司 | Composite graphite particles for lithium secondary battery and preparation method thereof |
-
2012
- 2012-10-30 CN CN201210422893.XA patent/CN103794765B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1547278A (en) * | 2003-12-12 | 2004-11-17 | 天津大学 | Putamen type carbon cathode material for lithium ion secondary battery and preparation method thereof |
| CN101053098A (en) * | 2004-08-30 | 2007-10-10 | 三菱化学株式会社 | Negative electrode material for nonaqueous secondary cells, negative electrode for nonaqueous secondary cells, and nonaqueous secondary cell |
| CN102593434A (en) * | 2011-01-11 | 2012-07-18 | 上海杉杉科技有限公司 | Composite graphite particles for lithium secondary battery and preparation method thereof |
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