CN108598392A - A kind of negative electrode of lithium ion battery carbon coating graphite rod and preparation method - Google Patents
A kind of negative electrode of lithium ion battery carbon coating graphite rod and preparation method Download PDFInfo
- Publication number
- CN108598392A CN108598392A CN201810279251.6A CN201810279251A CN108598392A CN 108598392 A CN108598392 A CN 108598392A CN 201810279251 A CN201810279251 A CN 201810279251A CN 108598392 A CN108598392 A CN 108598392A
- Authority
- CN
- China
- Prior art keywords
- graphite rod
- carbon coating
- lithium ion
- ion battery
- graphite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention provides a kind of negative electrode of lithium ion battery carbon coating graphite rod and preparation method, graphite hexagonal wire side and the graphite rod axial direction of the graphite rod are vertical relation；Degree of graphitization >=96%；About 10~30 μm of graphite rod diameter, length≤80 μm, draw ratio≤5, the surface coated carbon material of graphite rod are soft carbon.Carbon coating graphite rod preparation process includes the core process such as vapor deposition graphitization, shaping, cladding, negative electrode for lithium ion battery is made in gained carbon coating graphite rod, its 1C/1C recycles 3000 weeks capacity retention ratios and is higher than 80%, 6C/6C recycles 1000 weeks capacity retention ratios and is higher than 80%, is a negative material for having both long circulating, high-energy density, good dynamics performance.
Description
Technical field
The present invention relates to a kind of carbon coating graphite rod cathode material and preparation method, more particularly to a kind of high graphitization degree
Carbon coating graphite rod and preparation method.
Background technology
Electric vehicle be one across traffic, the energy, three big field of material novel industry, be currently under high speed development
Phase.The core of electric vehicle is lithium ion battery, and negative material is one of the basic factor for determining performance of lithium ion battery.It is electronic
The requirement of automobile negative material includes mainly：High circulation service life, high-energy density, power performance are excellent etc..It is well known that people
The cycle life for making graphite cathode material is much better than natural graphite, therefore, generally uses artificial graphite as electric vehicle negative
Pole material.
However, conventional artificial's graphite is but difficult to meet the needs of high-energy density and excellent power performance simultaneously, serious shadow
The development of domestic electric vehicle is rung.Have both the excellent negative material of high-energy density, power performance for exploitation, we select for the first time
Use a kind of carbon coating graphite bar material as lithium ion battery negative material.
Invention content
The purpose of the invention is to overcome the deficiencies of the prior art and provide a kind of negative electrode of lithium ion battery carbon coating stone
Inker, which is characterized in that the carbon coating graphite rod has following characteristics：Graphite hexagonal wire side is axially vertical close with graphite rod
System；Degree of graphitization >=96%；About 10~30 μm of graphite rod diameter, length≤80 μm, draw ratio≤5, the surface coated carbon of graphite rod
Material is soft carbon.
Further, the carbon coating graphite rod is prepared using following methods：Before being 6~9% forge by fugitive constituent
Coke is raw material, and sealing device is in graphite crucible；Then graphite crucible is placed in acheson furnace, it is right at 3000 DEG C~3300 DEG C
It is burnt before forging to carry out graphitization processing；After acheson furnace natural cooling, graphite crucible is taken out, by the life on the inside of graphite crucible pot cover
Long material scrapes to get to graphite fibre, and then the draw ratio of fiber is contracted within 5 by trimmer, VC mixing 1~6%
Pitch, then 1000 ~ 1500 DEG C of carbonization treatments, it is last it is screened, obtain target product except magnetic.
Further, it is described forge before it is burnt be oil system Raw needle coke, pitch green coke, oil green coke, mesocarbon microspheres life
It is burnt, one or more in mesophase pitch green coke.
Further, the mixing speed of VC mixing is 80~200rpm, 30~60min of mixing time.
Further, the carbonization asphalt softening point that uses of cladding is 200~280 DEG C, pitch type include asphalt with
One or more in coal tar pitch, the residing atmosphere that is carbonized is Ar or N2。
Further, the cathode of lithium battery slurry is prepared by following pulping process：
S1. carboxymethyl cellulose is dissolved in deionized water, uniform stirring, forms cmc soln；
S2. graphite rod is added in above-mentioned cmc soln, continues to stir, supplements deionized water while stirring；
S3. SBR emulsion is then added, continues to stir evenly, i.e., arrives very much cathode of lithium battery slurry.
Further, in step sl, the degree of substitution of the carboxymethyl cellulose is 0.85~0.9, and purity is higher than
99.5%。
Further, the cathode of lithium battery slurry is fabricated by the raw material of following weight percent：
Graphite rod 52.8~53.9%；
Carboxymethyl cellulose 0.6~1.1%；
SBR 0.6~1.1%；
Water 43.9~46.9%；
Carbon coating graphite rod of the present invention is under water system environmental system, using SBR bonding agents, by this carbon coating graphite rod system
At negative electrode for lithium ion battery, specific capacity can reach 360~365mAh/g, using 1.75~1.78g/cc of compacted density,
1C/1C recycles 3000 weeks capacity retention ratios and recycles 1000 weeks capacity retention ratios higher than 80% higher than 80%, 6C/6C.With existing routine
Artificial plumbago negative pole material is compared, and carbon coating graphite rod of the present invention is a long circulating, high-energy density, good of having both
The negative material of power performance can be used for high-end electric vehicle field.
Specific implementation mode
With reference to specific embodiment, invention is further described in detail.
Embodiment 1
Carbon coating graphite rod cathode material is prepared, steps are as follows：The oil system Raw needle coke of fugitive constituent 8% is installed on cylinder
In graphite crucible, crucible filling proportion is 80%；Graphite crucible is placed in acheson furnace, is carried out at graphitization at 3300 DEG C
Reason；After acheson furnace natural cooling, graphite crucible is taken out, the growth material on the inside of graphite crucible pot cover is taken out, you can
To graphite fibre, it is about 3 that shaping, which controls draw ratio,：1, the coal tar pitch that the softening point for being added 3% is 250 DEG C is mixed with VC mixing apparatus
40min is closed, mixture is then placed in N by mixing speed 120rpm2The lower 1050 DEG C of heat treatment of atmosphere, sieves after material cooling and removes
Magnetic obtains target product.
By material according to following process slurrying：
（Ⅰ）Gluing：It weighs in the CMC merging 1100.00g water of 20.00g and stirs 4.0h, mixing plant is using commercially available planetary
Blender, certainly/revolution speed is 30/25Hz.
（Ⅱ）Batch mixing in batches, it is 30/25Hz to stir certainly/revolution speed：
A) it is added and requires（1）In graphite rod 960.00g to the CMC solution, continue to stir 0.5h；
B) during addition 100g water will expect to graphite fibre, continue to stir 2h；
C) SBR emulsion is added to continue to stir 1.5h；
D) slurrying is completed.
Half-cell is 2025 type button cells, is lithium metal to electrode, detects its specific capacity；
Full battery is 503048PL, is domestic tertiary cathode material to electrode, detects its cycle performance and dynamic performance.
Comparative example 1
Conventional high-energy density artificial graphite material（Artificial graphite raw material：Needle coke）.Pole piece slurrying, battery assembling are the same as implementation
Example 1.
Comparative example 2
Artificial graphite material powered by conventional energy（Artificial graphite raw material：Carbonaceous mesophase spherules）.Pole piece slurrying, battery assembling are the same as implementation
Example 1.
Products obtained therefrom performance summary table：
| Specific capacity | Degree of graphitization | Limit compacted density | It is recommended that using compacted density | 1C/1C is recycled | 6C/6C is recycled | |
| Carbon coating graphite rod cathode material | 358mAh/g | 97.0% | 1.82g/cc | 1.75g/cc | 3000 weeks capacity retention ratios 88% | 1000 weeks capacity retention ratios 87% |
| Comparative example 1 | 355mAh/g | 95.5% | 1.80g/cc | 1.70g/cc | 1200 weeks battery end of life | 50 weeks battery end of life |
| Comparative example 2 | 335mAh/g | 91.0% | 1.53g/cc | 1.45g/cc | 3000 weeks capacity retention ratios 85% | 1000 weeks capacity retention ratios 81% |
It is found that carbon coating graphite rod cycle performance of the present invention is good, energy density is prepared higher than needle coke for comparison
Artificial graphite, high rate performance are better than artificial graphite prepared by carbonaceous mesophase spherules, are the high-end lithium-ion electrics of a power vehicle
Pond negative material.
Claims (6)
1. a kind of negative electrode of lithium ion battery carbon coating graphite rod, which is characterized in that the carbon coating graphite rod has following spy
Sign：Graphite hexagonal wire side is axially vertical relation with graphite rod；Degree of graphitization >=96%；About 10~30 μm of graphite rod diameter, length
≤ 80 μm, draw ratio≤5, the surface coated carbon material of graphite rod is soft carbon.
2. a kind of negative electrode of lithium ion battery carbon coating graphite rod according to claim 1, it is characterised in that：The carbon packet
When covering graphite rod for lithium ion battery negative material, 1C/1C recycles 3000 weeks capacity retention ratios and is recycled higher than 80%, 6C/6C
Capacity retention ratio is higher than 80% within 1000 weeks, is a negative material for having both long circulating, high-energy density, good dynamics performance.
3. a kind of negative electrode of lithium ion battery preparation method of carbon coating graphite rod, which is characterized in that include the following steps：It will wave
The preceding coke of forging that hair part is 6~9% is raw material, and sealing device is in graphite crucible；Then graphite crucible is placed in acheson furnace,
At 3000 DEG C~3300 DEG C graphitization processing is carried out to burnt before forging；After acheson furnace natural cooling, graphite crucible is taken out, by stone
Growth material on the inside of black crucible pot cover scrapes to get to fiber graphite, and then the draw ratio of fiber is contracted by trimmer
Within as low as 5, the pitch of VC mixing 1~6%, then 1000 ~ 1500 DEG C of carbonization treatments, it is last it is screened, target production is obtained except magnetic
Object.
4. a kind of preparation method of negative electrode of lithium ion battery carbon coating graphite rod according to claim 3, feature exist
In：It is described forge before it is burnt be oil system Raw needle coke, pitch green coke, oil green coke, mesocarbon microspheres green coke, mesophase pitch life
It is one or more in coke.
5. a kind of preparation method of negative electrode of lithium ion battery carbon coating graphite rod according to claim 3, feature exist
In：The mixing speed of VC mixing is 80~200rpm, 30~60min of mixing time.
6. a kind of preparation method of negative electrode of lithium ion battery carbon coating graphite rod according to claim 3, feature exist
In：For the asphalt softening point that carbonization cladding uses for 200~280 DEG C, pitch type includes one kind in asphalt and coal tar pitch
Or it is a variety of, the residing atmosphere that is carbonized is Ar or N2。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2017114868028 | 2017-12-30 | ||
| CN201711486802 | 2017-12-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108598392A true CN108598392A (en) | 2018-09-28 |
| CN108598392B CN108598392B (en) | 2020-08-21 |
Family
ID=63625078
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810279251.6A Active CN108598392B (en) | 2017-12-30 | 2018-03-31 | Preparation method of carbon-coated graphite rod for lithium ion battery cathode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108598392B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110739450A (en) * | 2019-10-15 | 2020-01-31 | 湖南中科星城石墨有限公司 | Process for coating graphite by mesophase pitches in edge contact manner |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05325946A (en) * | 1992-05-25 | 1993-12-10 | Yazaki Corp | Electrode for battery, its manufacuture and battery |
| CN102751472A (en) * | 2012-06-29 | 2012-10-24 | 上海锦众信息科技有限公司 | Cathode manufacturing method of lithium ion secondary battery |
| CN103165867A (en) * | 2011-12-12 | 2013-06-19 | 鹤岗市赛欧新材料有限责任公司 | Method for producing lithium ion battery negative electrode material by using petroleum coke |
| CN107369823A (en) * | 2017-07-25 | 2017-11-21 | 广东海洋大学 | A kind of lithium ion battery artificial composite cathode material of silicon/carbon/graphite and preparation method thereof |
-
2018
- 2018-03-31 CN CN201810279251.6A patent/CN108598392B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05325946A (en) * | 1992-05-25 | 1993-12-10 | Yazaki Corp | Electrode for battery, its manufacuture and battery |
| CN103165867A (en) * | 2011-12-12 | 2013-06-19 | 鹤岗市赛欧新材料有限责任公司 | Method for producing lithium ion battery negative electrode material by using petroleum coke |
| CN102751472A (en) * | 2012-06-29 | 2012-10-24 | 上海锦众信息科技有限公司 | Cathode manufacturing method of lithium ion secondary battery |
| CN107369823A (en) * | 2017-07-25 | 2017-11-21 | 广东海洋大学 | A kind of lithium ion battery artificial composite cathode material of silicon/carbon/graphite and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110739450A (en) * | 2019-10-15 | 2020-01-31 | 湖南中科星城石墨有限公司 | Process for coating graphite by mesophase pitches in edge contact manner |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108598392B (en) | 2020-08-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105938906B (en) | A kind of lithium ion battery artificial composite cathode material of silicon/carbon/graphite and preparation method thereof | |
| CN110148734B (en) | Hard carbon negative electrode material and preparation method and application thereof | |
| CN107342411B (en) | Preparation method of graphene-silicon-carbon lithium ion battery negative electrode material | |
| CN109599546A (en) | Asphalt carbon-coated natural mixed graphite material and method for preparing lithium ion battery cathode by using same | |
| CN102030326B (en) | Preparation method of graphite cathode material | |
| CN109860524A (en) | A kind of method of solid asphalt low temperature cladding preparation negative electrode material | |
| CN106169582B (en) | A kind of natural needle coke composite graphite negative electrode material production method | |
| CN109437184A (en) | A kind of high multiplying power lithium ion battery graphite cathode material and preparation method thereof | |
| CN110600715B (en) | Graphite cathode composite material of lithium ion battery and preparation method thereof | |
| CN110071274A (en) | Coat the processing technology that facture improves artificial plumbago negative pole material performance | |
| CN106602051A (en) | Preparation method of negative electrode slurry for lithium titanate battery | |
| CN105845935B (en) | A method of preparing battery graphite cathode material using special graphite powder | |
| WO2017177970A1 (en) | Coating agent, negative electrode material, lithium ion battery, and preparation method therefor | |
| CN109817925A (en) | Lithium ion secondary battery Si oxide composite negative pole material and preparation method | |
| CN108682787A (en) | A kind of electrodes of lithium-ion batteries and preparation method thereof | |
| CN112018366A (en) | Graphite negative electrode material of lithium ion battery and preparation method thereof | |
| CN114275777A (en) | Preparation method of high-graphitization-degree carbon-based material for lithium battery negative electrode | |
| CN109216822A (en) | The recovery method of negative electrode material of waste lithium ion battery | |
| CN108821275A (en) | A kind of lithium ion battery high capacity, high magnification graphite cathode material and preparation method thereof | |
| CN108598392A (en) | A kind of negative electrode of lithium ion battery carbon coating graphite rod and preparation method | |
| CN101327925B (en) | Production manufacturing method of carbon powder | |
| CN112573517A (en) | Preparation method of asphalt-based hard carbon-coated natural graphite negative electrode material | |
| CN102214821B (en) | Surface-modified graphitized intermediate-phase carbon micropowder and preparation method thereof | |
| CN108832124A (en) | The preparation method of graphite cathode material | |
| CN104157841A (en) | Preparation process of composite fiber electrode material for sodium-ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |