CN106252625A - A kind of preparation method of EV graphite negative material of lithium ion battery - Google Patents
A kind of preparation method of EV graphite negative material of lithium ion battery Download PDFInfo
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- CN106252625A CN106252625A CN201610741674.6A CN201610741674A CN106252625A CN 106252625 A CN106252625 A CN 106252625A CN 201610741674 A CN201610741674 A CN 201610741674A CN 106252625 A CN106252625 A CN 106252625A
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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
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- H01M4/364—Composites as mixtures
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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 present invention relates to graphite cathode material technical field, a kind of preparation method of EV graphite negative material of lithium ion battery, it is characterized in that using following preparation process: native graphite mixes with tar, native graphite is 60: 40～95: 5 with the weight ratio of tar；The native graphite isostatic cool pressing being blended with tar processes；Then heat treatment is carried out at hot VC machine with 300～700 DEG C；Being processed with hard pitch mixing carbonization by the native graphite being mixed with tar through Overheating Treatment, the temperature that carbonization processes is 1000～1900 DEG C, and the carbonization process time is 10～50 hours；Prepare the EV native graphite of surface modification interior solid.Compared with prior art, prepared product discharge capacity and first discharging efficiency are high, good cycle, the high comprehensive performance of its half-cell made for the present invention.
Description
Technical field
The present invention relates to graphite cathode material technical field, specifically a kind of EV graphite negative electrode of lithium ion battery material
The preparation method of material.
Background technology
Lithium ion battery compared with original battery, high with its energy density, have extended cycle life, the feature such as memory-less effect,
The most universal at aspects such as mobile phone, notebook computer and electric tools.In recent years, as effectively utilizing lithium ion battery
The new application of the features such as the little light weight of volume, carries out electric automobile (EV) Vehicular battery as motor-driven the most energetically
Exploitation, improve lithium ion battery negative material specific capacity, reduce irreversible capacity first, improve cyclical stability, always
It it is the emphasis of research and development.
The native graphite that ion secondary battery cathode material lithium uses has preferable layer structure, has the highest electric discharge and holds
Amount (close to theoretical capacity 372mAh/g), low cost but there is structural instability in it, easily cause the common embedding of solvent molecule so that it is
In charge and discharge process, synusia comes off, and causes cycle performance of battery poor, poor stability.
Therefore, for overcoming the deficiency of native graphite performance, prior art is all to be modified native graphite processing.Japan
Patent JP10294111 Colophonium carries out low temperature cladding to graphite Carbon Materials, must not melt process and slight powder after cladding
Broken, this method is difficult to be evenly coated.Japan Patent JP11246209 is 10～300 DEG C of temperature by graphite and hard charcoal granule
Impregnating in Colophonium or tar under degree, then carry out solvent separation and heat treatment, this method is difficult at graphite and hard carbon surface
Forming the bitumen layer with certain thickness high polymeric, the raising for native graphite structural stability is limited.Day
This patent JP2000003708 mechanically carries out rounding to graphite material, then carries out in heavy oil, tar or Colophonium
Dipping, then separate and wash, close with JP11246209 in terms of method for coating merely.Japan Patent JP2000182617 is
Using native graphite etc. and Colophonium or resin or its mixture Co carbonization, this method can reduce graphite material specific surface area,
But it is difficult to reach preferably to control on covered effect.Japan Patent JP2000243398 is the atmosphere pair utilizing asphalt pyrolysis to produce
Graphite material carries out surface process, and this method is unlikely, and make the to be modified form of material is greatly improved, thus makes electricity
The raising of performance is restricted.Japan Patent JP2002042816 carries out being coated with or use Colophonium phenol with aromatic hydrocarbons for raw material CVD
Urea formaldehyde is coated with, and this has similarity with JP2000182617 and JP2000283398 in effect.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, it is proposed that native graphite blended tars carries out isostatic cool pressing heat
The heating of VC machine, Surface coating hard pitch, the preparation method of carbonization, this preparation method productivity is high, and operation is simple, and product is obtaining
The most improved graphite negative material of lithium ion battery of cycle performance while high power capacity.
For achieving the above object, designing the preparation method of a kind of EV graphite negative material of lithium ion battery, its feature exists
In using following preparation process:
(1), native graphite mix with tar, the weight ratio of native graphite and tar is 60: 40～95: 5；
(2) the native graphite isostatic cool pressing, being blended with tar processes；
(3), then heat treatment is carried out at hot VC machine with 300～700 DEG C；
(4), being processed with hard pitch mixing carbonization by the native graphite being mixed with tar through Overheating Treatment, carbonization processes
Temperature be 1000～1900 DEG C, carbonization process the time be 10～50 hours；Prepare the EV of surface modification interior solid with natural
Graphite.
Described native graphite is spherical natural graphite.
Described tar is coal tar or petroleum heavy oil.
Described its mean diameter of EV native graphite is between 5～25 μm, and specific surface area is at 4.0m2/ below g, first
Discharge capacity is at more than 365mAh/g, and first charge-discharge efficiency is more than 95.0%, and 300 weeks discharge capacities of charge and discharge cycles keep
Rate is more than 85%
Compared with prior art, this preparation method can efficiently solve the problem that current material exists to the present invention, obtains
Through the modified natural graphite negative material that interior solid Surface coating, carbonization process, wherein native graphite Surface coating high temperature
Colophonium and charring process are simple and easy to do, and raw material sources are extensively and low cost；Due to have employed interior solid surface modification treatment,
The methods such as carbonization, prepared product discharge capacity and first discharging efficiency are high, good cycle, its half-cell made comprehensive
Function admirable.
Accompanying drawing explanation
Fig. 1 is the first charge-discharge curve of graphite cathode material of the present invention.
Fig. 2 is the scanning electron microscope (SEM) photograph of graphite cathode material of the present invention.
Fig. 3 is the cycle performance figure of graphite cathode material of the present invention.
Detailed description of the invention
In conjunction with embodiment, the present invention is further described.
Embodiment 1～7
The preparation method of embodiment 1～7 sees following table:
Raw material in embodiment 1～7 is conventional commercial product, and native graphite all uses spherical natural graphite.
It is described as follows as a example by embodiment 2:
By 20kg spherical natural graphite, mix with 2kg coal tar, put into isostatic cool pressing processing, discharging in cold isostatic press
After in hot VC machine, be warming up to 600 DEG C of heat treated, after cooling discharge according to 100: 4 weight ratios mixing hard pitches, by this sky
So graphite carries out carbonization high-temperature process 30 hours with 1500 DEG C, obtains graphite negative material of lithium ion battery.Half-cell capacity
368.7mAh/g, first efficiency 96.0%.
Used by the present invention, half-cell method of testing is: add conductive black in carboxymethyl cellulose (CMC) aqueous solution, so
Rear addition graphite sample, is eventually adding butadiene-styrene rubber (SBR), stirs, and slurry is coated on coating machine Copper Foil uniformly
On make pole piece.It is to be vacuum dried 4 hours in 110 DEG C of vacuum drying ovens that the pole piece coated is put into temperature, takes out pole piece at roller
Roll on press, standby.Simulated battery is assemblied in the German Braun glove box of applying argon gas and carries out, and electrolyte is 1M LiPF6
+ EC: DEC: DMC=1: 1: 1 (volume ratio), metal lithium sheet is to electrode.Volume test is surveyed at U.S. ArbinBT2000 type battery
Carrying out on examination instrument, charging/discharging voltage scope is 0.005 to 2.0V, and charge-discharge velocity is 0.1C.
Used by the present invention, full battery testing method is: the graphite of the embodiment of the present invention or comparative example makees negative pole, and cobalt acid lithium is made
Positive pole, 1M-LiPF6EC: DMC: EMC=1: 1: 1 (volume ratio) solution is made electrolyte assembling and is helped battery, tests 1C charge and discharge 300
Capability retention was more than 85.0%, as shown in Figure 3 week.
The performance parameter of each embodiment and comparative example is as shown in the table:
From data above it can be seen that discharge capacity comparative example and first efficiency are low, the natural stone of non-tar processing
The discharge capacity of ink is minimum, and for 354.1mAh/g, efficiency only has 90.2% first, circulates 300 weeks capability retentions and only reaches
70%.And using negative material prepared by method described in patent, capacity is more than 365mAh/g, and efficiency is more than 95.0%, circulates 300
Week, capability retention was all more than 85%, saw Fig. 1～Fig. 3.
Claims (4)
1. the preparation method of an EV graphite negative material of lithium ion battery, it is characterised in that use following preparation process:
(1), native graphite mix with tar, the weight ratio of native graphite and tar is 60: 40～95: 5；
(2) the native graphite isostatic cool pressing, being blended with tar processes；
(3), then heat treatment is carried out at hot VC machine with 300～700 DEG C；
(4), the native graphite being mixed with tar through Overheating Treatment is processed with hard pitch mixing carbonization, the temperature that carbonization processes
Degree is 1000～1900 DEG C, and the carbonization process time is 10～50 hours；Prepare the EV native graphite of surface modification interior solid.
The preparation method of a kind of EV graphite negative material of lithium ion battery the most as claimed in claim 1, it is characterised in that institute
The native graphite stated is spherical natural graphite.
The preparation method of a kind of EV graphite negative material of lithium ion battery the most as claimed in claim 1, it is characterised in that institute
The tar stated is coal tar or petroleum heavy oil.
The preparation method of a kind of EV graphite negative material of lithium ion battery the most as claimed in claim 1, it is characterised in that institute
Its mean diameter of EV native graphite stated is between 5～25 μm, and specific surface area is at 4.0m2/ below g, discharge capacity exists first
More than 365mAh/g, first charge-discharge efficiency more than 95.0%, 300 weeks discharge capacitances of charge and discharge cycles 85% with
On.
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| CN201610741674.6A CN106252625B (en) | 2016-08-26 | 2016-08-26 | Preparation method of graphite negative electrode material of lithium ion battery for EV (electric vehicle) |
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| CN201610741674.6A CN106252625B (en) | 2016-08-26 | 2016-08-26 | Preparation method of graphite negative electrode material of lithium ion battery for EV (electric vehicle) |
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| CN106252625B CN106252625B (en) | 2022-06-07 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108063229A (en) * | 2017-12-13 | 2018-05-22 | 深圳市贝特瑞新能源材料股份有限公司 | Natural graphite base modified composite material, its preparation method and the lithium ion battery comprising the modified composite material |
| CN108565443A (en) * | 2018-05-30 | 2018-09-21 | 武汉艾特米克超能新材料科技有限公司 | A kind of graphite cathode material and preparation method thereof, cathode pole piece and lithium ion battery |
| CN111463416A (en) * | 2020-04-14 | 2020-07-28 | 广东东岛新能源股份有限公司 | Low-cost low-expansion-rate long-circulation natural graphite-based composite material and preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108063229A (en) * | 2017-12-13 | 2018-05-22 | 深圳市贝特瑞新能源材料股份有限公司 | Natural graphite base modified composite material, its preparation method and the lithium ion battery comprising the modified composite material |
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| CN108565443A (en) * | 2018-05-30 | 2018-09-21 | 武汉艾特米克超能新材料科技有限公司 | A kind of graphite cathode material and preparation method thereof, cathode pole piece and lithium ion battery |
| CN111463416A (en) * | 2020-04-14 | 2020-07-28 | 广东东岛新能源股份有限公司 | Low-cost low-expansion-rate long-circulation natural graphite-based composite material and preparation method and application thereof |
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| CN106252625B (en) | 2022-06-07 |
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