CN110395725A - Quick-charging microcrystalline graphite negative electrode material and preparation method thereof - Google Patents
Quick-charging microcrystalline graphite negative electrode material and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 86
- 239000010439 graphite Substances 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000007773 negative electrode material Substances 0.000 title claims description 32
- 239000002699 waste material Substances 0.000 claims abstract description 32
- 239000011246 composite particle Substances 0.000 claims abstract description 25
- 238000005469 granulation Methods 0.000 claims abstract description 19
- 230000003179 granulation Effects 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 17
- 239000000654 additive Substances 0.000 claims abstract description 16
- 230000000996 additive effect Effects 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- 238000003763 carbonization Methods 0.000 claims abstract description 9
- 238000012216 screening Methods 0.000 claims abstract description 9
- 239000013081 microcrystal Substances 0.000 claims description 69
- 150000001875 compounds Chemical class 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 15
- 238000005087 graphitization Methods 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000002296 pyrolytic carbon Substances 0.000 claims description 7
- 239000011294 coal tar pitch Substances 0.000 claims description 6
- 239000002028 Biomass Substances 0.000 claims description 5
- 239000010426 asphalt Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000000320 mechanical mixture Substances 0.000 claims description 4
- 239000011295 pitch Substances 0.000 claims description 4
- 239000011800 void material Substances 0.000 claims description 4
- 238000004364 calculation method Methods 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 235000019580 granularity Nutrition 0.000 claims 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 239000010406 cathode material Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 28
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 14
- 229910001416 lithium ion Inorganic materials 0.000 description 14
- 239000002994 raw material Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 4
- 238000005253 cladding Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 230000003203 everyday effect Effects 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910021382 natural graphite Inorganic materials 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000013459 approach Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 235000021050 feed intake Nutrition 0.000 description 2
- 239000007770 graphite material Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 239000006253 pitch coke Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/205—Preparation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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
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Abstract
The invention discloses a preparation method of a quick-charging type microcrystalline graphite cathode material, which comprises the steps of mixing microcrystalline graphite waste with an additive, transferring the mixed material into granulation equipment, and carrying out composite granulation under the inert atmosphere condition to obtain composite particles; and after cooling the composite particles, carrying out twice classification by a classifier, transferring the twice-classified composite particles into a carbonization furnace for carbonization, and then naturally cooling, scattering, demagnetizing and screening to obtain the quick-charging microcrystalline graphite cathode material. The invention solves the problems that the microcrystalline graphite waste material in the prior art has overhigh specific surface area, low tap density and difficult manufacture of the fast-charging type cathode material.
Description
Technical field
The present invention relates to technical field of lithium ion battery negative more particularly to a kind of fast charging type micro crystal graphite cathode materials
Material and preparation method thereof.
Background technique
As the pace of life continues to accelerate and the explosive growth of information flow, people to everyday tools at one's side according to
Bad property is more and more stronger, while also to their performance, more stringent requirements are proposed.As most important Portable secondary power supply, lithium
Ion has been widely used in various everyday tools, such as mobile phone, I-Watch, laptop, electric car etc., however, mesh
The slow problem of the generally existing charging rate of preceding lithium ion battery, this leverages people when using corresponding everyday tools
Comfort.Therefore, exploitation fast charging type lithium ion battery has become current Main way.
Negative electrode material is the key that influence one of lithium ion battery rapid charging performance, negative electrode material most commonly used at present
For graphite type material.In order to improve the rapid charging performance of graphite cathode material, researcher is made that a large amount of trial, final to confirm
There are mainly two types of the approach for solving graphite material rapid charging performance, first is that selecting the square Jiaozhuo such as coal measures is the raw material of graphite, utilizes
The graphite cathode material with rapid charging performance can be obtained Deng the burnt isotropism in side；Second of approach is then post-processing, is led to
Crossing cladding or compound improves the quick embedding lithium ability of graphite material.
However, the side's of grade coke scheme is difficult to industrialization in a short time, this is primarily limited to country etc., and just coke is second-rate, no
It is practical, and side's coke such as foreign countries will not largely export to China then due to the limitation of nuclear graphite technical know-how.Therefore, it is domestic so far
There are no the graphite cathode materials of the burnt class in grade side.
Therefore, by the method for post-processing, just become focus concerned by people.In order to realize that the 10C of graphite cathode is fast
It fills, patent [JP10294111] and [CN105024043A] pass through cladding and the side being granulated using natural graphite as raw material respectively
Formula improves the rapid charging performance of graphite cathode, but the cycle performance of natural graphite itself is not as good as artificial graphite, therefore its
Smaller scope of application.Pitch coke or petroleum coke are raw material by patent [CN106981632A], by being first granulated the side coated afterwards
The problem of formula also obtains fast charging type graphite cathode material, which also avoids natural graphite Cycle Difference, however, the technique
Step is many and diverse, and production cost is higher, is only applicable to high-end lithium ion battery.
Micro crystal graphite intensity is low, and a large amount of fine powders are easy to produce in mechanical processing process, and powder yield processed is difficult more than 40%, and
About 60% fine powder of generation can be disposed admittedly as useless.The present invention is original with the micro crystal graphite waste material that graphite ore factory produces
Material, using the micro crystal graphite feature similar with grade side's close-burning structure, it is micro- to be prepared for high performance-price ratio fast charging type by compound technique
Brilliant graphite cathode material.
Summary of the invention
The present invention for overcome the deficiencies in the prior art, provides a kind of fast charging type micro crystal graphite negative electrode material and its preparation
Method.
The present invention is achieved by the following technical programs:
A kind of fast charging type micro crystal graphite negative electrode material, which is characterized in that the fast charging type micro crystal graphite negative electrode material includes
I, the granularity of micro crystal graphite is 2~6 μm, and degree of graphitization > 92%, impurity content are lower than 0.1%；
II, micro crystal graphite forms second particle by the connection of pyrolytic carbon, and the granularity of second particle is 12~20 μm；
III, the internal void of micro crystal graphite is pyrolyzed carbon and is filled up completely；
IV, specific surface area≤3m of micro crystal graphite second particle2/ g, tap density >=1.0g/cc；
V, there is the loose carbon-coating of one layer of 1~3nm thickness in the outermost layer of micro crystal graphite.
A kind of preparation method of fast charging type micro crystal graphite negative electrode material, comprising the following steps:
S1, micro crystal graphite waste material is mixed with additive, the additive includes asphalt, coal tar pitch, biomass drip
It is green；
S2, the material mixed is transferred in Granulation Equipments, carries out compound under inert atmosphere conditions, obtained compound
Particle；
It after S3, composite particles are cooling, is classified twice by grader, the granularity of the composite particles after being classified twice is
13~22 μm, PSD is 0.9~1.1.
S4, the composite particles after being classified twice are transferred in carbide furnace and are carbonized, natural cooling after carbonization, broken up,
Except magnetic, screening, fast charging type micro crystal graphite negative electrode material is obtained.
Preferably, a kind of preparation method of fast charging type micro crystal graphite negative electrode material, comprising the following steps:
S1, micro crystal graphite waste material is mixed with additive according to mass ratio 10:1.5~10:3, hybrid mode is VC mechanical
Mixing, wherein the granularity of the additive is 3~5 μm, and the additive includes asphalt, coal tar pitch, biomass pitch,
The softening point of the additive is 120~300 DEG C；
S2, the material mixed is transferred in Granulation Equipments, the compound in 400~600 DEG C and inert atmosphere is described
The rotation speed of Granulation Equipments is 10~90rpm, and granulation time is 2~8h, obtains composite particles；
It after S3, composite particles are cooling, is classified, is classified for the first time using 2# as target drop mouth twice by grader,
Second of classification is to be classified first time gained 2# again, compound after being classified twice using the 1# of grader as target drop mouth
The granularity of particle is 13~22 μm, and PSD is 0.9~1.1, and the PSD calculation method is (D90-D10)/D50；
S4, the composite particles after being classified twice are transferred in carbide furnace, it is fast with the speed of 5~10 DEG C/min under inert atmosphere
Speed is warming up to 350~500 DEG C, keeps the temperature 4~10h, is then to slowly warm up to 900~1250 with the heating rate of 1~3 DEG C/min
DEG C, natural cooling after 1h is kept the temperature, is broken up, except magnetic, screening, obtains fast charging type micro crystal graphite negative electrode material.
Preferably, in step s 2, the Granulation Equipments includes but is not limited to vertical retort, rotary drum furnace, horizontal retort etc..
Preferably, the inert atmosphere include but is not limited under the high temperature such as nitrogen, argon gas, helium not with micro crystal graphite, add
The inert gas for adding agent and additive thermal decomposition product to chemically react.
The invention discloses a kind of high performance-price ratio fast charging type micro crystal graphite negative electrode material and preparation method thereof, this method processes
Mainly are as follows: " micro crystal graphite waste material-compound-classification-carbonization-is sieved except magnetic ".Innovative point of the invention is main are as follows:
1. raw material selects:
The design feature of micro crystal graphite itself is very useful to the quick insertion of lithium ion, the especially lesser crystallite of granularity
Graphite waste, rapid charging performance can be more excellent.
It is raw material that the present invention selects micro crystal graphite waste material for the first time, can not only waste material be made to recycle, can also obtain high property
The fast charging type negative electrode material of valence ratio.
2. the grading technology after compound:
Why nobody uses micro crystal graphite waste material to prepare lithium ion battery fast charging type negative electrode material, and main cause is crystallite
The physical property of graphite waste is excessively poor, and being difficult to design effective process route improves the physical property of micro crystal graphite, such as than
Surface area and tap density.
The present invention improves the specific surface area of micro crystal graphite waste material by the way of compound, then passes through classifier again
Skill controls the size distribution of presoma by removal small grain size compound, to improve the tap density of presoma.For reality
Show this purpose, grading technology used in the present invention is two steps: the first step is to feed intake with the material of compound, grader
2# is target drop mouth, primarily to the bulky grain (1#) and part little particle (3#) in removal presoma (are mainly gone big
Particle)；Second step is to feed intake to be classified 2# resulting material, is classified again, using the 1# of grader as target drop mouth, mainly
Purpose is the little particle (2#, 3#) completely removed in presoma.
3. special carbonization technique
Micro crystal graphite specific surface area is excessively high, and tap density is relatively low.In order to solve these problems, the present invention has selected special
Carbonization technique, innovative point are the temperature increasing schedule being carbonized: firstly, presoma is rapidly heated to 350~500 DEG C and keeps the temperature one
Section time (internal void of micro crystal graphite is pyrolyzed carbon and is filled up completely), being then to slowly warm up to 900~1250 DEG C, (outer layer is formed
The loose carbon-coating of 1~3nm thickness), the liquid that 350~500 DEG C of incubation step can make additive be converted into flowing, and then fill
Internal void and outer surface to micro crystal graphite, in addition, the fugitive constituent in additive can escape to particle surface in the heat preservation later period, and
One layer of more loose cladding carbon-coating is formed in subsequent heating carbonisation.
4. the structure of micro crystal graphite negative electrode material
Micro crystal graphite granularity be 2~6 μm, by one layer of fine and close pyrolytic carbon by micro crystal graphite micro mist bonding be combined into it is secondary
Particle, the internal voids of micro crystal graphite are also pyrolyzed carbon and fill up；In the outermost layer of second particle, also one layer of 1~3nm is thick to be dredged
Loose carbon-coating.The structure is extremely beneficial to the quick embedding lithium of material.Firstly, outermost loose carbon-coating can play increase storage
The effect of liquid measure provides enough lithium sources for process of intercalation.Secondly, fine and close pyrolytic carbon be distributed in micro crystal graphite surface and
It is internal, it is well known that migration velocity of the lithium ion in pyrolytic carbon be far faster than graphite layers, therefore, fine and close pyrolytic carbon
Just as fast-ionic conductor, lithium ion is delivered directly to the surface and inside of micro crystal graphite, lithium ion is greatly shortened and exists
Diffusion time in particle.Combining closely for pyrolytic carbon and micro crystal graphite, also effectively reduces the specific surface area (≤3m of particle2/
G), tap density >=1.0g/cc of gained powder.
The present invention provides a kind of new processes that lithium ion battery fast charging type negative electrode material is prepared using micro crystal graphite waste material
Method solves existing by the process route of " micro crystal graphite waste material-compound-classification-carbonization-is sieved except magnetic "
Micro crystal graphite waste material specific surface area is excessively high in technology, tap density is relatively low, is difficult to make the problem of fast charging type negative electrode material.This hair
Bright selection micro crystal graphite waste material is raw material, can not only waste material be made to recycle, and prepared fast charging type negative electrode material has production
Feature at low cost, that specific surface area is small, tap density is high, rapid charging performance and cycle performance are excellent, specific performance data are shown in implementation
Contrast table in example.
Specific embodiment
The present invention is further illustrated combined with specific embodiments below.
Embodiment 1
The asphalt (4.8 μm of granularity) that the micro crystal graphite waste material of degree of graphitization 93.2% is 120 DEG C with softening point is pressed
According to 10:3 VC mechanical mixture.
The material mixed is transferred in vertical retort, the compound in 400 DEG C, nitrogen atmosphere, material is in Granulation Equipments
In rotation speed be 90rpm, granulation time 3h obtains composite particles.
After composite particles are cooling, it is classified twice by grader, classification is using 2# as target drop mouth for the first time, and second
Secondary classification is to be classified first time gained 2# again, using the 1# of grader as target drop mouth.Composite particles after being classified twice
Granularity be 13~22 μm, PSD be 0.9~1.1, the PSD calculation method be (D90-D10)/D50。
Finally, the composite particles after being classified twice are transferred in carbide furnace, it is fast with the speed of 10 DEG C/min under nitrogen atmosphere
Speed is warming up to 350 DEG C, keeps the temperature 10h, is then to slowly warm up to 900 DEG C with the heating rate of 1 DEG C/min, keeps the temperature naturally cold after 1h
But, it is broken up after, except magnetic, screening, 1# sample is made.
Embodiment 2
By the micro crystal graphite waste material of degree of graphitization 93.2% and softening point be 280 DEG C coal tar pitch (3.9 μm of granularity) according to
10:1.5 VC mechanical mixture.
The material mixed is transferred in rotary drum furnace, the compound in 600 DEG C and argon atmosphere, material is in Granulation Equipments
In rotation speed be 15rpm, granulation time 8h.
After composite particles are cooling, it is classified twice by grader, process is similar to Example 1.
Finally, the composite particles after being classified twice are transferred in carbide furnace, it is quick with the speed of 5 DEG C/min under argon atmosphere
500 DEG C are warming up to, 4h is kept the temperature, is then to slowly warm up to 1250 DEG C with the heating rate of 3 DEG C/min, keeps the temperature natural cooling after 1h,
It is broken up after and, except 2# sample is made in magnetic, screening.
Embodiment 3
The biomass pitch (3.3 μm of granularity) for being 200 DEG C by the micro crystal graphite waste material of degree of graphitization 93.2% and softening point
According to 10:2.3 VC mechanical mixture.
The material mixed is transferred in horizontal chamber furnace (oven), the compound in 500 DEG C and argon atmosphere, material is in Granulation Equipments
In rotation speed be 40rpm, granulation time 5h.
After composite particles are cooling, it is classified twice by grader F1, process is similar to Example 1.
Finally, the composite particles after being classified twice are transferred in carbide furnace, it is quick with the speed of 7 DEG C/min under argon atmosphere
450 DEG C are warming up to, 7h is kept the temperature, is then to slowly warm up to 1100 DEG C with the heating rate of 2 DEG C/min, keeps the temperature natural cooling after 1h,
It is broken up after and, except 3# sample is made in magnetic, screening.
Comparative example
The micro crystal graphite waste material of degree of graphitization 93.2% is mixed with the coal tar pitch that softening point is 280 DEG C according to 10:1.5,
It is graphitized, broken up, except contrast sample is made in magnetic, screening.
1~3# sample and comparative example data comparison are as shown in the table.
As seen from the above table, products of the present invention has production cost low, and specific surface area is small, tap density is high, fast charge
Performance and the excellent feature of cycle performance.
The present invention uses the process route of " micro crystal graphite waste material-compound-classification-carbonization-is sieved except magnetic ".Its
The thinking of innovation is as follows:
(1) micro crystal graphite waste material has the characteristics that crystallite dimension is small, isotropic hardening, is suitable as fast charging type negative electrode material
Raw material.
(2) micro crystal graphite waste material pattern itself is irregular, and specific surface area is high, and jolt ramming is relatively low, can not be directly as lithium ion
Cell negative electrode material, by simply coating the disadvantages mentioned above for being difficult to improve micro crystal graphite waste material, therefore the present invention has selected again
Close the technique being granulated, due to can use additives more more than cladding process in compound technique, compare surface area and
The improvement of jolt ramming can be more obvious.
(3) grading technology is increased after granulation, can be controlled the size distribution of presoma very by the technique
In narrow range, which can further improve the physical property of micro crystal graphite composite particles.
(4) last heat treatment mode uses carbonization technique rather than the graphitization technique of high energy consumption, entire product processing
Process is simple, to ensure that the low cost of product.In addition, the rapid charging performance of negative electrode material obtained by carbonization technique is better than graphitization
Product, therefore, the preparation process is again it is advantageously ensured that the rapid charging performance of product.
The present invention provides a kind of new processes that lithium ion battery fast charging type negative electrode material is prepared using micro crystal graphite waste material
Method solves existing by the process route of " micro crystal graphite waste material-compound-classification-carbonization-is sieved except magnetic "
Micro crystal graphite waste material specific surface area is excessively high in technology, tap density is relatively low, is difficult to make the problem of fast charging type negative electrode material.This hair
Bright selection micro crystal graphite waste material is raw material, can not only waste material be made to recycle, and prepared fast charging type negative electrode material has production
Feature at low cost, that specific surface area is small, tap density is high, rapid charging performance and cycle performance are excellent.
The above is only a preferred embodiment of the present invention, protection scope of the present invention is not limited merely to above-mentioned implementation
Example.It should be pointed out that for those skilled in the art, without departing from the principles of the present invention several change
Into and retouching, also should be regarded as protection scope of the present invention.The available prior art of each component part being not known in the present embodiment
It is realized.
Claims (5)
1. a kind of fast charging type micro crystal graphite negative electrode material, which is characterized in that the fast charging type micro crystal graphite negative electrode material includes
I, the granularity of micro crystal graphite is 2~6 μm, and degree of graphitization > 92%, impurity content are lower than 0.1%；
II, micro crystal graphite forms second particle by the connection of pyrolytic carbon, and the granularity of second particle is 12~20 μm；
III, the internal void of micro crystal graphite is pyrolyzed carbon and is filled up completely；
IV, specific surface area≤3m of micro crystal graphite second particle2/ g, tap density >=1.0g/cc；
V, there is the loose carbon-coating of one layer of 1~3nm thickness in the outermost layer of micro crystal graphite.
2. a kind of preparation method of fast charging type micro crystal graphite negative electrode material, which comprises the following steps:
S1, micro crystal graphite waste material is mixed with additive, the additive includes asphalt, coal tar pitch, biomass pitch；
S2, the material mixed is transferred in Granulation Equipments, carries out compound under inert atmosphere conditions, obtain compound
Grain；
After S3, composite particles are cooling, be classified twice by grader, the granularities of the composite particles after being classified twice for 13~
22 μm, PSD is 0.9~1.1.
S4, the composite particles after being classified twice are transferred in carbide furnace and are carbonized, natural cooling after carbonization, broken up, except magnetic,
Screening, obtains fast charging type micro crystal graphite negative electrode material.
3. a kind of preparation method of fast charging type micro crystal graphite negative electrode material according to claim 2, which is characterized in that including
Following steps:
S1, micro crystal graphite waste material being mixed with additive according to mass ratio 10:1.5~10:3, hybrid mode is VC mechanical mixture,
Wherein, the granularity of the additive is 3~5 μm, and the additive includes asphalt, coal tar pitch, biomass pitch, described to add
The softening point for adding agent is 120~300 DEG C；
S2, the material mixed is transferred in Granulation Equipments, the compound in 400~600 DEG C and inert atmosphere, the granulation
The rotation speed of equipment is 10~90rpm, and granulation time is 2~8h, obtains composite particles；
After S3, composite particles are cooling, it is classified twice by grader, classification is using 2# as target drop mouth for the first time, and second
Secondary classification is to be classified first time gained 2# again, the composite particles using the 1# of grader as target drop mouth, after being classified twice
Granularity be 13~22 μm, PSD be 0.9~1.1, the PSD calculation method be (D90-D10)/D50；
S4, the composite particles after being classified twice are transferred in carbide furnace, are quickly risen under inert atmosphere with the speed of 5~10 DEG C/min
Temperature keeps the temperature 4~10h to 350~500 DEG C, is then to slowly warm up to 900~1250 DEG C with the heating rate of 1~3 DEG C/min, protects
Natural cooling after warm 1h is broken up, except magnetic, screening, obtains fast charging type micro crystal graphite negative electrode material.
4. a kind of preparation method of fast charging type micro crystal graphite negative electrode material according to claim 2, it is characterised in that: in step
In rapid S2, Granulation Equipments used is vertical retort, rotary drum furnace or horizontal retort.
5. a kind of preparation method of fast charging type micro crystal graphite negative electrode material according to claim 2, it is characterised in that: in step
In rapid S2 and S4, the inert gas in the inert atmosphere is nitrogen, argon gas or helium.
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