CN105836728B - A kind of preparation method of lithium ion battery pitch hard charcoal negative electrode material - Google Patents
A kind of preparation method of lithium ion battery pitch hard charcoal negative electrode material Download PDFInfo
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- CN105836728B CN105836728B CN201610164454.1A CN201610164454A CN105836728B CN 105836728 B CN105836728 B CN 105836728B CN 201610164454 A CN201610164454 A CN 201610164454A CN 105836728 B CN105836728 B CN 105836728B
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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
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2006/40—Electric properties
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- 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 discloses a kind of preparation method of lithium ion battery pitch hard charcoal negative electrode material, comprises the following steps that and cold primer-oil 1) is made in commercial sulfonated gilsonite and deionized water, filter out undissolved pitch particle, obtains clear water-soluble cold primer-oil；2) graphite microparticles are added in the cold primer-oil that step 1) obtains；3) the graphite pitch solution for obtaining step 2) carries out mist projection granulating, obtains the pitch hard charcoal microballoon that partial size is 1-51 μm；4) lithium ion battery pitch hard charcoal negative electrode material will be obtained after the heating heating, drying of pitch hard charcoal microballoon obtained by step 3).The cost of material that the present invention uses is cheap, from a wealth of sources；In entire production process without adding any organic solvent；Pitch hard charcoal particle diameter distribution is controllable；Preparation process is easily industrialized production.Prepared pitch hard charcoal negative electrode material has excellent embedding lithium, de- lithium ability, is suitable for power lithium-ion battery.
Description
Technical field
The present invention relates to field of lithium ion battery material technologies, and it is negative to be especially to provide a kind of lithium ion battery pitch hard charcoal
The preparation method of pole material.
Background technique
At present, application of the lithium ion battery in electric vehicle is the hot spot in Study on Li-ion batteries.To by lithium ion
Battery is used in electric automobiles, and the condition for needing to meet is: when high current recycles, stability is good, and reversible specific capacity is high.Existing rank
Section, the negative electrode materials such as graphite, hard charcoal, soft carbon, lithium titanate are the main study subjects in power battery field.For hard charcoal, it is based on
Its stable structure, excellent multiplying power property, cyclical stability, the cycle life of length, high safety and capacity retention ratio exist
It remains to obtain the holding of higher level under high current, and has and be conducive to Li+The microstructure of disengaging, so hard carbon material is more suitable
Together in the application of dynamic field.
Currently, the raw material of lithium ion battery hard charcoal negative electrode material mainly has resinae raw material, biomass material and mine
Object petrochemical material etc..Due to the difference of precursor construction property and preparation method, the microstructure and electricity of prepared hard carbon material
Chemical property is widely different.In current preparation method, crosslinking agent is added in some need, and is related to material mixing and pre- charcoal
Change process, process are cumbersome；Some uses hydro-thermal method, the condition of high temperature and pressure, the high requirements on the equipment, poor safety performance；Have
Need to be added catalyst, product needs to wash and dry etc., higher cost.In addition, the lithium ion prepared by biological material
Cell negative electrode material is unfavorable for large-scale production due to the limitation of the factors such as raw material sources and cost.
Summary of the invention
In view of this, the present invention is in view of the existing deficiencies of the prior art, the purpose of the present invention is to provide a kind of lithium ions
The battery preparation method of pitch hard charcoal negative electrode material, this method is simple and easy, environmentally protective, is easy to scale industrial production,
Obtained pitch hard charcoal negative electrode material specific capacity is high, can be in fast charging and discharging under high current, good cycle.
To achieve the above object, the present invention is using following technical solution: a kind of lithium ion battery pitch hard charcoal cathode
The preparation method of material, comprises the following steps that
It 1) is that cold primer-oil is made in 1:50-400 according to mass ratio by commercial sulfonated gilsonite and deionized water, in 500-
After stirring 0.5-5h under 2000r/min revolving speed, undissolved pitch particle is filtered out, obtains clear water-soluble cold primer-oil；
2) graphite microparticles are added in the cold primer-oil that step 1) obtains, are stirred under 500-2000r/min revolving speed
It after 0.5-5h, is added in sand mill, grinds 1-8h, obtain graphite pitch solution；
3) the graphite pitch solution for obtaining step 2) is 80-120 DEG C in inlet air temperature, and sample introduction flow velocity is 100-500L/
H, blower frequency carry out mist projection granulating under conditions of being 40-60Hz, obtain the pitch hard charcoal microballoon that partial size is 1-51 μm；
4) under the protection of nitrogen or inert gas, by pitch hard charcoal microballoon obtained by step 3) with the heating of 1-5 DEG C/min
Speed is warming up to 400 DEG C, keeps the temperature 1h, is then warming up to 500-1200 DEG C with the heating rate of 0.5-3 DEG C/min, keeps the temperature 3-20h,
Then cooled to room temperature obtains lithium ion battery pitch hard charcoal negative electrode material.
As a preferred embodiment, the water solubility of the commercial sulfonated gilsonite is 50-100%, pH value 7-8, and density is big
In 0.95g/cm3, softening point is greater than 150 degree.
As a preferred embodiment, the graphite is at least one of artificial graphite or the micro mist of natural graphite.
It as a preferred embodiment, is 1:10-100 according to the asphalt quality ratio in graphite microparticles and cold primer-oil
As a preferred embodiment, sand mill revolving speed is 2500-2800r/min in the step 2), wherein 0.3- is added
The zirconium oxide bead of 0.4um.
The present invention has obvious advantages and beneficial effects compared with the existing technology, specifically: the raw material that the present invention uses
It is cheap, it is from a wealth of sources；In entire production process without adding any organic solvent；Pitch hard charcoal particle diameter distribution is controllable；System
Standby process is easily industrialized production.Prepared pitch hard charcoal negative electrode material has excellent embedding lithium, de- lithium ability, is applicable in
In power lithium-ion battery.
Detailed description of the invention
Fig. 1 is the electron-microscope scanning figure of embodiments of the present invention 1.
Specific embodiment
Embodiment 1
A kind of lithium ion battery preparation method of pitch hard charcoal negative electrode material, comprises the following steps that
1) it is that cold primer-oil is made in 1:400 according to mass ratio by commercial sulfonated gilsonite and deionized water, turns in 500r/min
After the lower stirring 5h of speed, undissolved pitch particle is filtered out, obtains clear water-soluble cold primer-oil；The commercialization sulfonated gilsonite
Water solubility be 100%, pH value 7-8, density be greater than 0.95g/cm3, softening point is greater than 150 degree.
2) graphite microparticles are added in the cold primer-oil that step 1) obtains, after stirring 0.5h under 500r/min revolving speed,
It is added in sand mill, which is 2800r/min, and the zirconium oxide bead for being added 0.4 micron carries out grinding 1h, obtains
Graphite pitch solution；The graphite is at least one of artificial graphite or the micro mist of natural graphite；According to graphite microparticles with
Asphalt quality ratio in cold primer-oil is 1:10.
3) the graphite pitch solution for obtaining step 2) is 80 DEG C in inlet air temperature, and sample introduction flow velocity is 500L/h, blower frequency
Rate carries out mist projection granulating under conditions of being 40Hz, obtains the pitch hard charcoal microballoon that partial size is 1-51 μm；
4) under the protection of nitrogen or inert gas, by pitch hard charcoal microballoon obtained by step 3) with the heating speed of 5 DEG C/min
Degree is warming up to 400 DEG C, keeps the temperature 1h, is then warming up to 500 DEG C with the heating rate of 3 DEG C/min, keeps the temperature 20h, then natural cooling
To room temperature, lithium ion battery pitch hard charcoal negative electrode material is obtained.
Embodiment 2
A kind of lithium ion battery preparation method of pitch hard charcoal negative electrode material, comprises the following steps that
1) it is that cold primer-oil is made in 1:50 according to mass ratio by commercial sulfonated gilsonite and deionized water, turns in 2000r/min
After the lower stirring 0.5h of speed, undissolved pitch particle is filtered out, obtains clear water-soluble cold primer-oil；The commercialization sulfonation drip
Green water solubility is 50%, and pH value 7-8, density is greater than 0.95g/cm3, softening point is greater than 150 degree.
2) graphite microparticles are added in the cold primer-oil that step 1) obtains, after stirring 0.5h under 2000r/min revolving speed,
It is added in sand mill, which is 2800r/min, and the zirconium oxide bead that 0.3um is added carries out grinding 8h, obtains stone
Black cold primer-oil；The graphite is artificial graphite；It is 1:100 according to the asphalt quality ratio in graphite microparticles and cold primer-oil.
3) the graphite pitch solution for obtaining step 2) is 100 DEG C in inlet air temperature, and sample introduction flow velocity is 100L/h, blower frequency
Rate carries out mist projection granulating under conditions of being 40-60Hz, obtains the pitch hard charcoal microballoon that partial size is 1-51 μm；
4) under the protection of nitrogen or inert gas, by pitch hard charcoal microballoon obtained by step 3) with the heating of 1-5 DEG C/min
Speed is warming up to 400 DEG C, keeps the temperature 1h, is then warming up to 1200 DEG C with the heating rate of 0.5 DEG C/min, keeps the temperature 3h, then natural
It is cooled to room temperature, obtains lithium ion battery pitch hard charcoal negative electrode material.
Embodiment 3
A kind of lithium ion battery preparation method of pitch hard charcoal negative electrode material, comprises the following steps that
1) it is that cold primer-oil is made in 1:100 according to mass ratio by commercial sulfonated gilsonite and deionized water, turns in 1000r/min
After the lower stirring 3.5h of speed, undissolved pitch particle is filtered out, obtains clear water-soluble cold primer-oil；The commercialization sulfonation drip
Green water solubility is 60%, and pH value 7-8, density is greater than 0.95g/cm3, softening point is greater than 150 degree.
2) graphite microparticles are added in the cold primer-oil that step 1) obtains, after stirring 4.5h under 1000r/min revolving speed,
It is added in sand mill, which is 2500r/min, and the zirconium oxide bead that 0.3um is added carries out grinding 6h, obtains stone
Black cold primer-oil；The graphite is the micro mist of natural graphite；It is 1 according to the asphalt quality ratio in graphite microparticles and cold primer-oil:
50。
3) the graphite pitch solution for obtaining step 2) is 120 DEG C in inlet air temperature, and sample introduction flow velocity is 300L/h, blower frequency
Rate carries out mist projection granulating under conditions of being 50Hz, obtains the pitch hard charcoal microballoon that partial size is 1-51 μm；
4) under the protection of nitrogen or inert gas, by pitch hard charcoal microballoon obtained by step 3) with the heating of 1-5 DEG C/min
Speed is warming up to 400 DEG C, keeps the temperature 1h, is then warming up to 860 DEG C with the heating rate of 2.5 DEG C/min, keeps the temperature 10h, then natural
It is cooled to room temperature, obtains lithium ion battery pitch hard charcoal negative electrode material.
Embodiment 4
A kind of lithium ion battery preparation method of pitch hard charcoal negative electrode material, comprises the following steps that
1) it is that cold primer-oil is made in 1:200 according to mass ratio by commercial sulfonated gilsonite and deionized water, turns in 1000r/min
After the lower stirring 2h of speed, undissolved pitch particle is filtered out, obtains clear water-soluble cold primer-oil；The commercialization sulfonation drip
Green water solubility is 70%, and pH value 7-8, density is greater than 0.95g/cm3, softening point is greater than 150 degree.
2) graphite microparticles are added in the cold primer-oil that step 1) obtains, after stirring 4h under 1500r/min revolving speed, are added
Enter into sand mill, which is 2800r/min, and the zirconium oxide bead that 0.3-0.4um is added carries out grinding 4h, obtains
Graphite pitch solution；The graphite is artificial graphite；It is 1:30 according to the asphalt quality ratio in graphite microparticles and cold primer-oil.
3) the graphite pitch solution for obtaining step 2) is 90 DEG C in inlet air temperature, and sample introduction flow velocity is 400L/h, blower frequency
Rate carries out mist projection granulating under conditions of being 50Hz, obtains the pitch hard charcoal microballoon that partial size is 1-51 μm；
4) under the protection of nitrogen or inert gas, by pitch hard charcoal microballoon obtained by step 3) with the heating of 1-5 DEG C/min
Speed is warming up to 400 DEG C, keeps the temperature 1h, is then warming up to 800 DEG C with the heating rate of 2 DEG C/min, keeps the temperature 6h, then natural cooling
To room temperature, lithium ion battery pitch hard charcoal negative electrode material is obtained.
Electrochemical property test is carried out to product obtained by Examples 1 to 4:
For the performance of the lithium ion battery negative material of detection negative electrode material of the present invention, tested with half-cell test method,
With the negative electrode material of above embodiments: SBR (solid content 50%): CMC: Super-p=95.5: 2: 1.5: 1 (weight ratio), add suitable
Deionized water reconciliation pulp is measured, be coated on copper foil and negative electrode tab, electrolyte was made in dry 12 hours in vacuum oven
It is 1MLiPF6/EC+DEC+DMC=1: 1: 1, microporous polypropylene membrane is diaphragm, is lithium piece to electrode, is assembled into battery.In LAND
Battery test system carries out constant current charge-discharge experiment, and charging/discharging voltage is limited in 0.01~3.0V, the charge and discharge computerizedd control
Electric cabinet carries out the acquisition and control of data, test temperature: 25 DEG C and 60 DEG C.Obtained data are as shown in table 1 below.
The negative electrode material performance that table 1 lists different embodiments compares.
Electronic Speculum test is scanned to embodiment 1, is schemed from the SEM in attached drawing 1 it is observed that through above-mentioned preparation method system
At asphalt hard carbon material pattern based on oval particle, partial size is in 1-50um.
As it can be seen from table 1 the efficiency for charge-discharge of pitch hard carbon cathode material of the invention is high, high rate performance and cyclicity
It can be well, it can be achieved that the requirement of lithium ion battery fast charging and discharging under high current.
The above described is only a preferred embodiment of the present invention, be not intended to limit the scope of the present invention,
Therefore any trickle amendment, equivalent variations and modification made to the above embodiment according to the technical essence of the invention, still
Belong in the range of technical solution of the present invention.
Claims (3)
1. a kind of lithium ion battery preparation method of pitch hard charcoal negative electrode material, it is characterised in that: comprise the following steps that
It 1) is that cold primer-oil is made in 1:50-400 according to mass ratio by commercial sulfonated gilsonite and deionized water, in 500-2000r/
After stirring 0 .5-5h under min revolving speed, undissolved pitch particle is filtered out, obtains clear water-soluble cold primer-oil；
2) graphite microparticles are added in the cold primer-oil that step 1) obtains, stir 0 .5- under 500-2000r/min revolving speed
It after 5h, is added in sand mill, grinds 1-8h, obtain graphite pitch solution；According to the pitch in graphite microparticles and cold primer-oil
Mass ratio is 1:10-100；Sand mill revolving speed is 2500-2800r/min, wherein the zirconium oxide bead of 0 .3-0 .4 μm is added；
3) the graphite pitch solution for obtaining step 2) is 80-120 DEG C in inlet air temperature, and sample introduction flow velocity is 100-500L/h, wind
Unit frequency carries out mist projection granulating under conditions of being 40-60Hz, obtains the pitch hard charcoal microballoon that partial size is 1-51 μm；
4) under the protection of nitrogen or inert gas, by pitch hard charcoal microballoon obtained by step 3) with the heating rate of 1-5 DEG C/min
400 DEG C are warming up to, 1h is kept the temperature, is then warming up to 500-1200 DEG C with the heating rate of 0 .5-3 DEG C/min, keeps the temperature 3-20h, so
Cooled to room temperature afterwards obtains lithium ion battery pitch hard charcoal negative electrode material.
2. the preparation method of a kind of lithium ion battery pitch hard charcoal negative electrode material according to claim 1, it is characterised in that:
The water solubility of the commercialization sulfonated gilsonite is 50-100%, and pH value 7-8, density is greater than 0 .95g/cm3, softening point is greater than 150
Degree.
3. the preparation method of a kind of lithium ion battery pitch hard charcoal negative electrode material according to claim 1, it is characterised in that:
The graphite is at least one of artificial graphite or the micro mist of natural graphite.
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| CN110265660A (en) * | 2019-06-21 | 2019-09-20 | 内蒙古大学 | A kind of preparation method of cell negative electrode material sulfonated gilsonite base hard charcoal |
| CN113725415B (en) * | 2021-08-31 | 2023-03-24 | 常州高态信息科技有限公司 | Power type graphite-silicon oxide composite material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186292A (en) * | 2006-11-22 | 2008-05-28 | 辽宁工程技术大学 | Method for preparing carbon cathode material and lithium iron battery using the material |
| CN101582503A (en) * | 2008-05-14 | 2009-11-18 | 天津市铁诚电池材料有限公司 | Negative electrode material of lithium ion battery with graphite covered by asphalt and preparation method thereof |
| CN102646819A (en) * | 2012-05-03 | 2012-08-22 | 天津大学 | Preparation method of carbon-coated natural crystalline flake graphite composite for lithium ion batteries |
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2016
- 2016-03-22 CN CN201610164454.1A patent/CN105836728B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186292A (en) * | 2006-11-22 | 2008-05-28 | 辽宁工程技术大学 | Method for preparing carbon cathode material and lithium iron battery using the material |
| CN101582503A (en) * | 2008-05-14 | 2009-11-18 | 天津市铁诚电池材料有限公司 | Negative electrode material of lithium ion battery with graphite covered by asphalt and preparation method thereof |
| CN102646819A (en) * | 2012-05-03 | 2012-08-22 | 天津大学 | Preparation method of carbon-coated natural crystalline flake graphite composite for lithium ion batteries |
Non-Patent Citations (2)
| Title |
|---|
| 磺化沥青包覆石墨制备复合材料;滕艳杰等;《化学工程与装备》;20150131(第1期);第14-15页 |
| 磺化沥青包覆石墨用作锂离子电池负极材料;张翠等;《电源技术》;20150531;第139卷(第5期);第889-891页 |
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