CN108807995A - A kind of lithium ion battery graphite cathode material and preparation method thereof - Google Patents
A kind of lithium ion battery graphite cathode material and preparation method thereof Download PDFInfo
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- CN108807995A CN108807995A CN201810877817.5A CN201810877817A CN108807995A CN 108807995 A CN108807995 A CN 108807995A CN 201810877817 A CN201810877817 A CN 201810877817A CN 108807995 A CN108807995 A CN 108807995A
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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
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Abstract
The invention discloses a kind of lithium ion battery graphite cathode materials and preparation method thereof, are related to technical field of lithium ion.The lithium ion battery is prepared according to the following steps with graphite cathode material：Graphite precursor material is crushed, Shape correction obtains graphite presoma fine powder；It graphite presoma fine powder and binder is put into stirrer for mixing is uniformly placed on to be granulated in hot coating reaction kettle and obtain particulate material；Particulate material is sieved to obtain oversize 1 and minus mesh 1, then screening obtains oversize 2 and minus mesh 2 after oversize 1 is broken up processing；Minus mesh 1 and minus mesh 2 are carried out to graphitization processing respectively to obtain graphitization sample 1 successively and be graphitized sample 2；Graphitization sample is sieved, except magnetic, screening；It is blended graphitization sample to obtain graphite cathode material.Characteristic of the graphite cathode material with high power capacity, high-pressure solid, preparation process is simple, easy to operate, it is easy to accomplish industrialization.
Description
Technical field
The present invention relates to technical field of lithium ion more particularly to a kind of lithium ion battery graphite cathode material and its
Preparation method.
Background technology
Lithium ion battery is with its operating voltage height, energy density height, efficiency for charge-discharge height, memory-less effect, self discharge are small,
The advantages that green non-pollution, it is considered to be the 21 century optimal energy.
Negative material is one of lithium ion battery critical material, at present large-scale commercial mainly include artificial graphite,
Natural graphite and mesocarbon microspheres etc..Artificial graphite occupies larger because having both excellent cycle performance and higher capacity
The market share, main application is in the 3C class products such as smart mobile phone, super basis.In recent years, artificial graphite is removed produces for 3C classes
Product are also more applied in power battery, in order to promote stand-by time and course continuation mileage, 3C class product batteries and power battery
Develop to high-energy density, this requires artificial plumbago negative pole materials must have higher specific discharge capacity and compacted density,
To realize the promotion of lithium-ion battery system energy density.
Compared with natural graphite, the degree of graphitization of artificial graphite is relatively low, and crystallinity is relatively low, therefore capacity is relatively low；
And easily rebound after artificial graphite compacting, compacted density is relatively relatively low.The factor for influencing material capacity and compacting mainly has matrix
The influence of selection, degree of graphitization, size distribution, pattern, orientation, the OI values of material etc..For influence factor, a kind of tool is developed
The artificial plumbago negative pole material for having high graphitization degree, high power capacity, high-pressure solid is this field problem urgently to be resolved hurrily.
Invention content
To solve the above-mentioned problems, a kind of lithium ion battery graphite cathode material of present invention offer and preparation method thereof,
By crushing, shaping, granulation, graphitization, screening, except magnetic, blending, the graphite with high power capacity, high-pressure solid is prepared in the present invention
Negative material, preparation process is simple, easy to operate, it is easy to accomplish industrialization.
In order to achieve the above purpose, technical scheme is as follows：
Present invention aims at a kind of preparation method of lithium ion battery graphite cathode material is provided, have according to the following steps
Body carries out：
(1) it crushes：Graphite precursor material is crushed, Shape correction obtains the graphite that average grain diameter is 5~13 μm
Presoma fine powder；
(2) it mixes：Graphite presoma fine powder and binder are put into stirrer for mixing and uniformly obtain mixture；
(3) it is granulated：Mixture is placed in hot coating reaction kettle, is granulated to obtain particulate material in an inert atmosphere；
(4) it sieves：Particulate material is placed on sieve and is sieved, oversize 1 and minus mesh 1 are obtained, by oversize 1 through beating
It dissipates to be placed on sieve after handling and be sieved, obtain oversize 2 and minus mesh 2；
(5) it is graphitized：The progress graphitization processing of minus mesh 1 is obtained into graphitization sample 1, minus mesh 2 is graphitized
Processing obtains graphitization sample 2；
(6) screening removes magnetic：Graphitization sample 1 and graphitization sample 2 are sieved, except magnetic, screening；
(7) it blends：It is blended graphitization sample to obtain graphite cathode material.
Preferably, in the step (1), the graphite precursor material is needle coke.
Preferably, in the step (1), grinding mode be 80 crush, one kind of roll mill；Training system is that 60 machines are whole
Shape, one kind of stream energy shaping.
Preferably, in the step (2), the graphite presoma fine powder is by weight percentage with binder：Before graphite
Drive body fine powder 80-92%, binder 8-20%.
Preferably, in the step (2), the binder is one kind in hard pitch, mid temperature pitch, the binder
Granularity is 2~6 μm.
Preferably, in the step (3), the reaction kettle is one kind in vertical response kettle, horizontal reacting kettle, described lazy
Property atmosphere be nitrogen.
Preferably, described to break up processing as one or both of VC mixing, fusion, the sieve in the step (4)
Mesh number is 100~500 mesh.
Preferably, in the step (7), by screening except being graphitized sample 1 and sieving except the graphitization sample after magnetic after magnetic
Product 2 are 9 in proportion:1~6 is blended using research of grade-suit theory, obtains negative material.
Preferably, in the step (7), screening is removed to the graphitization sample 1 after magnetic and primary graphitizing particle in proportion
It is 9:1~6 is blended using research of grade-suit theory, obtains negative material；The primary graphitizing particle is needle coke or petroleum coke
The average grain diameter of the product obtained through crushing, shaping, graphitization processing, the primary graphitizing particle is 8~14 μm.
Another object of the present invention is to improve a kind of lithium ion battery graphite cathode material.
Due to using above-mentioned technical solution, the beneficial effects of the invention are as follows：
1) research of grade-suit theory is utilized, the offspring or primary particle different by blending grain size adjust the grain of final products
Degree distribution, to improve compacted density, reduce expansion improve cycle performance, negative material obtained have high power capacity, high-pressure solid,
The excellent feature of cycle performance.
2) it after being granulated, once sieves obtained oversize 1 grain size after breaing up and slightly reduces, then screened obtain under sieve
Expect 2, forms graphitization sample 2 after graphitization, be then blended into the graphitization sample 1 of minus mesh 1, on the one hand can improve and make
The yield of grain process, reduces cost, on the other hand can make the particle diameter distribution of minus mesh more reasonable by grading, to also improve
The compacted density of material.And the preparation process of the present invention is simple, easy to operate, it is easy to accomplish industrialization.
Description of the drawings
Fig. 1 schemes for lithium ion battery graphite cathode material SEM of the present invention；
Fig. 2 is lithium ion battery graphite cathode material particle size distribution figure of the present invention.
Specific implementation mode
Firstly, it is necessary to which explanation, will illustrate lithium ion battery stone of the present invention by way of example below
The characteristics of black negative material and preparation method thereof and advantage etc., however what all descriptions were intended merely to illustrate, without answering
It is understood as forming any restrictions to the present invention.
The embodiment just provided below by this come to lithium ion battery graphite cathode material of the present invention and its
Preparation method illustrates.
Embodiment 1
The graphite cathode material preparation method of lithium ion battery described in the present embodiment is specific according to the following steps to carry out：
Graphite precursor material is crushed using roll mill, is then 8 μ obtaining average grain diameter using 60 machine Shape corrections
The graphite presoma fine powder of m；It is uniform that 90% graphite presoma fine powder and 10% binder are put into stirrer for mixing
To mixture；Mixture is placed in heat cladding vertical response kettle again, is granulated to obtain particulate material in a nitrogen atmosphere；General
Pellet, which is placed on sieve, is sieved to obtain oversize 1 and minus mesh 1, and by oversize 1, to be placed on sieve enterprising after breaing up processing
Oversize 2 and minus mesh 2 can be obtained in row screening, and the sieve mesh number is 200 mesh；The progress graphitization processing of minus mesh 1 is obtained
It is graphitized sample 1, the progress graphitization processing of minus mesh 2 is obtained into graphitization sample 2；It will graphitization sample 1 and graphitization sample 2
It is sieved, except magnetic, screening；By screening except the graphitization sample 1 after magnetic is in proportion with the graphitization sample 2 sieved after removing magnetic
9:2 are blended using research of grade-suit theory, obtain negative material.The all gram volumes of head of negative material obtained by the present embodiment are
350mAh/g, compacted density 1.68g/cm3。
Above-mentioned graphite precursor material is needle coke；Above-mentioned binder is hard pitch, and the binder granularity is 2~6 μ
m。
It is described to break up processing as one or both of VC mixing, fusion in the step (4).
Embodiment 2
The graphite cathode material preparation method of lithium ion battery described in the present embodiment is specific according to the following steps to carry out：
Graphite precursor material is crushed using roll mill, is then 12 obtaining average grain diameter using stream energy Shape correction
μm graphite presoma fine powder；It is uniform that 80% graphite presoma fine powder and 20% binder are put into stirrer for mixing
To mixture；Mixture is placed in heat cladding vertical response kettle again, is granulated to obtain particulate material in a nitrogen atmosphere；General
Pellet, which is placed on sieve, is sieved to obtain oversize 1 and minus mesh 1, and by oversize 1, to be placed on sieve enterprising after breaing up processing
Oversize 2 and minus mesh 2 can be obtained in row screening, and the sieve mesh number is 400 mesh；The progress graphitization processing of minus mesh 1 is obtained
It is graphitized sample 1, the progress graphitization processing of minus mesh 2 is obtained into graphitization sample 2；It will graphitization sample 1 and graphitization sample 2
It is sieved, except magnetic, screening；It is 9 in proportion that screening is removed to the graphitization sample 1 after magnetic with primary graphitizing particle:5 utilize grade
It is blended with theory, obtains negative material.The all gram volumes of head of negative material obtained by the present embodiment are 353.3mAh/g, compacting
Density is 1.70g/cm3
Above-mentioned primary graphitizing particle is the product that needle coke or petroleum coke are obtained through crushing, shaping, graphitization processing, on
The average grain diameter for stating primary graphitizing particle is 10 μm；Above-mentioned graphite precursor material is needle coke；Above-mentioned binder is high temperature
Pitch, the binder granularity are 2~6 μm.
It is described to break up processing as one or both of VC mixing, fusion in the step (4).
Embodiment 3
The graphite cathode material preparation method of lithium ion battery described in the present embodiment is specific according to the following steps to carry out：
Graphite precursor material is crushed using roll mill, is then 12 obtaining average grain diameter using stream energy Shape correction
μm graphite presoma fine powder；It is uniform that 85% graphite presoma fine powder and 15% binder are put into stirrer for mixing
To mixture；Mixture is placed in heat cladding vertical response kettle again, is granulated to obtain particulate material in a nitrogen atmosphere；General
Pellet, which is placed on sieve, is sieved to obtain oversize 1 and minus mesh 1, and by oversize 1, to be placed on sieve enterprising after breaing up processing
Oversize 2 and minus mesh 2 can be obtained in row screening, and the sieve mesh number is 500 mesh；The progress graphitization processing of minus mesh 1 is obtained
It is graphitized sample 1, the progress graphitization processing of minus mesh 2 is obtained into graphitization sample 2；By screening except the graphitization sample 1 after magnetic
It is 9 in proportion with primary graphitizing particle:5 are blended using research of grade-suit theory, obtain negative material.Cathode obtained by the present embodiment
The all gram volumes of head of material are 351.6mAh/g, compacted density 1.71g/cm3
Above-mentioned primary graphitizing particle is the product that needle coke or petroleum coke are obtained through crushing, shaping, graphitization processing, institute
The average grain diameter for stating primary graphitizing particle is 12 μm.Above-mentioned graphite precursor material is needle coke.Above-mentioned binder is medium temperature
Pitch, the binder granularity are 2~6 μm.
It is described to break up processing as one or both of VC mixing, fusion in the step (4).
Currently, all gram volumes of the head of common lithium ion battery negative material are 345.2mAh/g, compacted density is
1.60g/cm3, and all gram volumes of the head for the lithium ion battery that above-described embodiment 1~3 is prepared and compacted density are apparently higher than
Conventional lithium-ion battery negative material.
Claims (10)
1. a kind of preparation method of lithium ion battery graphite cathode material, which is characterized in that specific according to the following steps to carry out：
(1) it crushes：Graphite precursor material is crushed, Shape correction obtains the graphite forerunner that average grain diameter is 5~13 μm
Body fine powder；
(2) it mixes：Graphite presoma fine powder and binder are put into stirrer for mixing and uniformly obtain mixture；
(3) it is granulated：Mixture is placed in hot coating reaction kettle, is granulated to obtain particulate material in an inert atmosphere；
(4) it sieves：Particulate material is placed on sieve and is sieved, oversize 1 and minus mesh 1 are obtained, by oversize 1 through breaing up place
It is placed on sieve and is sieved after reason, obtain oversize 2 and minus mesh 2；
(5) it is graphitized：The progress graphitization processing of minus mesh 1 is obtained into graphitization sample 1, minus mesh 2 is subjected to graphitization processing
Obtain graphitization sample 2；
(6) screening removes magnetic：Graphitization sample 1 and graphitization sample 2 are sieved, except magnetic, screening；
(7) it blends：It is blended graphitization sample to obtain graphite cathode material.
2. the preparation method of lithium ion battery graphite cathode material according to claim 1, it is characterised in that：The step
(1) in, the graphite precursor material is needle coke.
3. the preparation method of lithium ion battery graphite cathode material according to claim 1, it is characterised in that：The step
(1) in, grinding mode be 80 crush, one kind of roll mill；Training system is one kind of 60 machine shapings, stream energy shaping.
4. the preparation method of lithium ion battery graphite cathode material according to claim 1, it is characterised in that：The step
(2) in, the graphite presoma fine powder is by weight percentage with binder：Graphite presoma fine powder 80-92%, binder 8-
20%.
5. the preparation method of lithium ion battery graphite cathode material according to claim 1, it is characterised in that：The step
(2) in, the binder is one kind in hard pitch, mid temperature pitch, and the binder granularity is 2~6 μm.
6. the preparation method of lithium ion battery graphite cathode material according to claim 1, it is characterised in that：The step
(3) in, the reaction kettle is one kind in vertical response kettle, horizontal reacting kettle, and the inert atmosphere is nitrogen.
7. the preparation method of lithium ion battery graphite cathode material according to claim 1, it is characterised in that：The step
(4) in, described to break up processing as one or both of VC mixing, fusion, the sieve mesh number is 100~500 mesh.
8. the preparation method of lithium ion battery graphite cathode material according to claim 1, it is characterised in that：The step
(7) in, by screening except being graphitized sample 1 and sieving except the graphitization sample 2 after magnetic is 9 in proportion after magnetic:1~6 utilizes grade
It is blended with theory, obtains negative material.
9. the preparation method of lithium ion battery graphite cathode material according to claim 1, it is characterised in that：The step
(7) in, it is 9 in proportion that screening is removed to the graphitization sample 1 after magnetic with primary graphitizing particle:1~6 is carried out using research of grade-suit theory
Blending, obtains negative material；The primary graphitizing particle is that needle coke or petroleum coke are obtained through crushing, shaping, graphitization processing
The average grain diameter of the product arrived, the primary graphitizing particle is 8~14 μm.
10. cathode material made from a kind of preparation method of lithium ion battery graphite cathode material according to claims 1 to 9
Material.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110649256A (en) * | 2019-10-17 | 2020-01-03 | 石家庄尚太科技有限公司 | Single-particle and secondary-particle mixed high-energy-density graphite negative electrode material and preparation method thereof |
| CN111446421A (en) * | 2020-04-02 | 2020-07-24 | 广东凯金新能源科技股份有限公司 | Graphite negative electrode for low-magnetic-impurity lithium battery and preparation method |
| CN112421031A (en) * | 2020-11-24 | 2021-02-26 | 宁德新能源科技有限公司 | Electrochemical device and electronic device |
| CN113526500A (en) * | 2021-07-20 | 2021-10-22 | 安徽科达新材料有限公司 | Preparation method of high-performance artificial graphite negative electrode material |
| CN115924906A (en) * | 2022-12-16 | 2023-04-07 | 广东凯金新能源科技股份有限公司 | Treatment method of graphite oversize product, artificial graphite and application |
| CN116239382A (en) * | 2022-12-23 | 2023-06-09 | 合肥国轩新材料科技有限公司 | Preparation method of high-pressure compact composite graphite and lithium ion battery |
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| CN115924906A (en) * | 2022-12-16 | 2023-04-07 | 广东凯金新能源科技股份有限公司 | Treatment method of graphite oversize product, artificial graphite and application |
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