CN108483437A - It is a kind of using ethylene coke as lithium cell carbon cathode material of raw material and preparation method thereof - Google Patents

It is a kind of using ethylene coke as lithium cell carbon cathode material of raw material and preparation method thereof Download PDF

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Publication number
CN108483437A
CN108483437A CN201810224466.8A CN201810224466A CN108483437A CN 108483437 A CN108483437 A CN 108483437A CN 201810224466 A CN201810224466 A CN 201810224466A CN 108483437 A CN108483437 A CN 108483437A
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China
Prior art keywords
offspring
primary particle
coke
average grain
grain diameter
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CN201810224466.8A
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Chinese (zh)
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CN108483437B (en
Inventor
臧文平
李琳慈
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Anhui brocade Carbon Technology Development Co., Ltd.
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TIANJIN JINMEI CARBON MATERIAL SCIENCE AND TECHNOLOGY DEVELOPMENT Co Ltd
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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
    • 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
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention provides a kind of using ethylene coke as the preparation method of the lithium cell carbon cathode material of raw material, belongs to field of lithium ion battery.It is characterised in that it includes the composite particles of primary particle and offspring, primary particle is expected after using average grain diameter D50 to be forged for 1 ~ 15 μm of ethylene coke, and offspring expects to mix according to 5 with pitch after using average grain diameter D50 to forge for 1 10 μm of ethylene coke:1~10:1 ratio carries out pyroreaction after being mixed admittedly and is made.Material prepared by method using the present invention, have the advantages that specific capacity is high, have extended cycle life, specific capacity is up to 360mAh/g, recycle 460 95% or more capacity retention ratios, in addition isotropism degree is preferable, compacted density is high, especially has lower production cost, is expected to have good application prospect in fields such as power vehicles.

Description

It is a kind of using ethylene coke as lithium cell carbon cathode material of raw material and preparation method thereof
Technical field
With ethylene coke it is original more particularly to one kind the present invention relates to a kind of lithium cell carbon cathode material and preparation method thereof Lithium cell carbon cathode material of material and preparation method thereof, the carbon cathode material prepared by this method form a kind of high power capacity high pressure In fact, good cycle, primary particle at low cost and the compound graphite material of offspring.
Background technology
Lithium ion battery negative material mainly has two kinds of artificial graphite and natural graphite based on Carbon Materials.Artificial graphite Raw material have petroleum coke, pitch coke, needle coke, coal etc., using petroleum coke, pitch coke be the cathode graphite of raw material have cost Advantage low, stability is good, but have the shortcomings that capacity is relatively low, in terms of being mainly used in low and middle-end power battery, with needle-shaped Jiaozhuo is that the cathode graphite material capacity of raw material is higher, can be applied in terms of high-end power battery, but processing performance is slightly poor, and And needle coke higher price, have no apparent competitive advantage.Other carbon negative pole materials, such as mesocarbon microspheres are from pitch It extracts, has the advantages that particle shape is good, irreversible capacity loss is low, cycle life is stablized, but there is also be produced into The low insufficient disadvantage of this height, discharge capacity.Natural graphite starting material is at low cost, but there are tap densities for the natural graphite of sheet Disadvantage low, specific surface area is high is not suitable for using directly as negative material.There is no natural graphite negative electrode material modified Irreversible capacity loss is very high for the first time, can generally reach 10 %, is embedded in altogether in cycle since solvent occurs, capacity is caused to decline Subtract the problems such as fast.Although having clear improvement by rounding and the natural graphite electrical property of surface treatment, but still there is capacitance to decline Subtract the very fast and higher disadvantage of production cost.
Invention content
The technical problem to be solved by the present invention is to keep the property indices of product to reach the high-end cathode of market demands On the basis of the performance indicator of material, production cost is greatly lowered.
The present invention provides a kind of lithium ion battery negative material being prepared as a raw material with high-quality ethylene coke, including primary The composite particles of particle and offspring, it is characterised in that：Primary particle uses average grain diameter D50It is forged for 1 ~ 15 μm of ethylene coke After expect, offspring use average grain diameter D50Material mixes progress pyroreaction with pitch and is made after being forged for 1-10 μm of ethylene coke, The preparation of wherein offspring is according to ethylene coke and pitch according to 5:1~10:After 1 ratio is mixed admittedly, through walking as follows Suddenly it is made：
1）Polymerisation, 300~600 minutes reaction time are carried out within the temperature range of 200~700 DEG C；
2）Charing process is carried out at a temperature of 900~1200 DEG C.
Final products are primary particle and offspring according to 1:4~4:After 1 ratio is mixed admittedly, through walking as follows Suddenly it is made：
1）Graphitization processing is carried out at a temperature of 2700~3000 DEG C；
2）Screening removes magnetic.
It is a kind of using ethylene coke as the lithium cell carbon cathode material preparation method of raw material, include the following steps：
1, average grain diameter D is made in material after forging ethylene coke50For 1 ~ 15 μm of primary particle；
2, average grain diameter D is made in material after forging ethylene coke50For 1-10 μm of primary particle, with pitch according to 5:1~10:1 ratio Example is mixed admittedly, and polymerisation, 300~600 minutes reaction time are carried out within the temperature range of 200~700 DEG C；
3, charing process is carried out at a temperature of 900~1200 DEG C；
4, by primary particle and offspring according to 1:4~4:1 ratio is mixed admittedly, at a temperature of 2700~3000 DEG C Graphitization processing is carried out, screening removes magnetic.
This carbon cathode material that the present invention obtains have isotropism degree is good, specific capacity is high, compacted density is high, recycle the longevity It orders the advantages that long, especially there is lower production cost.
Marginal data
Fig. 1 is the scanning electron microscope diagram of the charcoal cathode prepared according to the embodiment of the present invention 4.
Fig. 2 is the charging and discharging curve figure of the charcoal cathode prepared according to the embodiment of the present invention 4.
Specific implementation mode
Embodiment 1-10 products are detected using Q/TEZI01-2001 electrochemistry capacitances testing standard, result is such as Under：
By detection, the properties of product of embodiment 1-10 have reached the index of commercially available high-end artificial plumbago negative pole material, due to adopting It is raw material with high-quality ethylene Jiaozhuo, it is larger to reduce production cost.

Claims (2)

1. a kind of lithium cell carbon cathode material, including primary particle and offspring, it is characterised in that：
Primary particle uses average grain diameter D50Expect after being forged for 1 ~ 15 μm of ethylene coke, offspring uses average grain diameter D50For 1-10 μm ethylene coke forge after expect to mix according to 5 with pitch:1~10:1 ratio carries out pyroreaction after being mixed admittedly and is made, drip Blueness uses one kind or mixture of selected from coal tar pitch and petroleum asphalt, offspring to be made through following steps：
1）Polymerisation, 300~600 minutes reaction time are carried out within the temperature range of 200~700 DEG C；
2）Charing process is carried out at a temperature of 900~1200 DEG C；
Final products are primary particle and offspring according to 1:4~4:After 1 ratio is mixed admittedly, through following steps system At：
1）Graphitization processing is carried out at a temperature of 2700~3000 DEG C；
2）Screening removes magnetic.
2. it is a kind of using ethylene coke as the lithium cell carbon cathode material preparation method of raw material, include the following steps：
Average grain diameter D is made in material after ethylene coke is forged50For 1 ~ 15 μm of primary particle；
Average grain diameter D is made in material after ethylene coke is forged50For 1-10 μm of primary particle, with pitch according to 5:1~10:1 ratio into The solid solid mixing of row, carries out polymerisation within the temperature range of 200~700 DEG C, 300~600 minutes reaction time, 900~ Charing process is carried out at a temperature of 1200 DEG C, and offspring is made；
By primary particle and offspring according to 1:4~4:1 ratio is mixed admittedly, at a temperature of 2700~3000 DEG C into Row graphitization processing, screening remove magnetic.
CN201810224466.8A 2018-03-19 2018-03-19 Lithium battery carbon negative electrode material taking ethylene coke as raw material and preparation method thereof Active CN108483437B (en)

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CN201810224466.8A CN108483437B (en) 2018-03-19 2018-03-19 Lithium battery carbon negative electrode material taking ethylene coke as raw material and preparation method thereof

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CN201810224466.8A CN108483437B (en) 2018-03-19 2018-03-19 Lithium battery carbon negative electrode material taking ethylene coke as raw material and preparation method thereof

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CN108483437B CN108483437B (en) 2021-07-09

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021190650A1 (en) * 2020-03-27 2021-09-30 宁德时代新能源科技股份有限公司 Secondary battery, battery module comprising same, battery pack, and device

Citations (5)

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Publication number Priority date Publication date Assignee Title
US6482547B1 (en) * 1998-05-21 2002-11-19 Samsung Display Devices Co., Ltd. Negative active material for lithium secondary battery and lithium secondary battery using the same
CN101108729A (en) * 2006-07-20 2008-01-23 天津市铁诚电池材料有限公司 Method for manufacturing artificial plumbago negative pole material of lithium ion power cell
CN105489893A (en) * 2015-10-28 2016-04-13 江西正拓新能源科技股份有限公司 Graphite anode material for lithium-ion battery and preparation method of graphite anode material
CN105938906A (en) * 2016-06-18 2016-09-14 湖南星城石墨科技股份有限公司 Artificial graphite composite negative electrode material for lithium-ion battery and preparation method of artificial graphite composite negative electrode material
CN107758653A (en) * 2016-08-17 2018-03-06 宁波杉杉新材料科技有限公司 A kind of preparation method of lithium ion battery composite particles graphite cathode material

Patent Citations (5)

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Publication number Priority date Publication date Assignee Title
US6482547B1 (en) * 1998-05-21 2002-11-19 Samsung Display Devices Co., Ltd. Negative active material for lithium secondary battery and lithium secondary battery using the same
CN101108729A (en) * 2006-07-20 2008-01-23 天津市铁诚电池材料有限公司 Method for manufacturing artificial plumbago negative pole material of lithium ion power cell
CN105489893A (en) * 2015-10-28 2016-04-13 江西正拓新能源科技股份有限公司 Graphite anode material for lithium-ion battery and preparation method of graphite anode material
CN105938906A (en) * 2016-06-18 2016-09-14 湖南星城石墨科技股份有限公司 Artificial graphite composite negative electrode material for lithium-ion battery and preparation method of artificial graphite composite negative electrode material
CN107758653A (en) * 2016-08-17 2018-03-06 宁波杉杉新材料科技有限公司 A kind of preparation method of lithium ion battery composite particles graphite cathode material

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Title
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021190650A1 (en) * 2020-03-27 2021-09-30 宁德时代新能源科技股份有限公司 Secondary battery, battery module comprising same, battery pack, and device

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Address after: 242000 Northwest Intersection of Tieshan Road Qingyijiang Avenue, Xuancheng Economic and Technological Development Zone, Xuancheng City, Anhui Province

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Applicant before: Tianjin Jinmei Carbon Material Science and Technology Development Co., Ltd.

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