CN102887504B - A kind of preparation method of carbon material for lithium ion battery cathode - Google Patents
A kind of preparation method of carbon material for lithium ion battery cathode Download PDFInfo
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- CN102887504B CN102887504B CN201210357660.6A CN201210357660A CN102887504B CN 102887504 B CN102887504 B CN 102887504B CN 201210357660 A CN201210357660 A CN 201210357660A CN 102887504 B CN102887504 B CN 102887504B
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Abstract
The invention discloses the preparation method of a kind of carbon material for lithium ion battery cathode, comprise the steps: in concentrated sulphuric acid rapid after graphite heating or concentrated nitric acid solution, add surfactant sonic oscillation, make the fully oxidized separation of graphite, again product is reduced, i.e. form the mono-layer graphite of high yield, then mono-layer graphite ball milling powder is broken into powder body graphite；After being processed in sodium hydroxide solution by powder body graphite, then sulfuric acid solution carries out pickling, then wash and be dried；Graphite composite powder after going the removal of impurity is modified；Under the atmosphere of CO (carbon monoxide converter) gas, modified powder graphite is carried out surface reduction process；Graphite composite powder after reduction treatment is carried out thin film process.Cathode of lithium battery material with carbon element prepared by the present invention, has good electric conductivity, cyclical stability, and when lithium ion battery, capacity is high, and service life is long.
Description
Technical field
The present invention relates to a kind of ion cathode material lithium preparation method, particularly relate to the preparation method of a kind of carbon material for lithium ion battery cathode.
Background technology
Lithium ion battery is high due to its energy density, and good cycle has had been obtained for being widely applied since its commercialization, gradually instead of the electrochmical power sources such as traditional lead-acid battery.In particular with day by day highlighting of energy and environment problem, New Energy Industry has obtained increasing attention.
Lithium ion battery is mainly made up of positive pole, negative pole, barrier film and electrolyte, can wherein prepare that energy density is high, power density high, have extended cycle life, the negative material of low cost be one of branch that this research direction is most active, is also that can restriction lithium ion battery continue the determiner to the development of the high-tech area such as hybrid vehicle, space flight and aviation.
The material with carbon elements such as graphite, as lithium ion battery negative material, the most in use exist: poor with solvent compatibility, high-rate performance is poor, and during first charge-discharge, the common embedding because of solvent molecule makes carbon-coating peeling-off, and electrode life reduces.The micronization of the negative pole carbon material that this exopathogenic factor charge and discharge cycles causes, may result in the reduction of this carbon material electric conductivity.
Therefore, in the urgent need to providing a kind of good conductivity, circulation ability is strong, the lithium ion battery negative pole carbon material of life-span length.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of carbon material for lithium ion battery cathode, the lithium ion battery of carbon material for negative electrode prepared by use the method has the features such as good conductivity, capacity height, length in service life.
To achieve these goals, the preparation method of a kind of carbon material for lithium ion battery cathode that the present invention provides comprises the steps:
Step 1, pretreating graphite
By in the concentrated sulphuric acid or the concentrated nitric acid solution that immerse rapidly less than 10 DEG C after graphite heating to 100-300 DEG C, add surfactant sonic oscillation, make the fully oxidized separation of graphite, again product is reduced, i.e. form the mono-layer graphite of high yield, then by powder body graphite that mono-layer graphite ball mill pulverizing to particle diameter is 5-10 μm；
Step 2, removes the impurity in graphite
Powder body graphite is processed 2-4 hour in 500-550 DEG C in the sodium hydroxide solution that concentration is 50-70%, then carries out pickling in the sulfuric acid solution that concentration is 50-60%, then wash and be dried, to remove the impurity in powder body graphite；
Step 3, is modified the graphite composite powder after going the removal of impurity
Graphite composite powder is mixed homogeneously with the nickel oxide accounting for graphite quality 4-6%, put in carbide furnace, the programming rate of carbide furnace is set as 100 DEG C/h begin to warm up, stop when reaching 1100 DEG C heating up, keep 6 hours at such a temperature, then in 1500-1700 DEG C of catalyzed graphitization 1-2 hour under a nitrogen, modified powder graphite is obtained；
Step 4, carries out reduction treatment to modified graphite powder body
Under the atmosphere of CO (carbon monoxide converter) gas, in 500-700 DEG C, modified powder graphite is carried out surface reduction and process 2-4 hour；
Step 5, carries out thin film process to the graphite composite powder after reduction treatment
Use chemical vapour deposition technique, graphite composite powder after reduction treatment is carried out peplos, making its Surface coating last layer thickness is that the carbon of 1-2 μm is to improve initial coulomb efficiency, i.e. prepare lithium-ion electric negative pole pond material with carbon element, wherein chemical vapor deposition conditions: carbon source is the alkane of C1 ~ C5, depositing temperature is 700-900 DEG C, and sedimentation time is 2-4 hour.
Wherein, carbon source described in step 5 is preferably the alkane of C1 ~ C3, more preferably ethane.
Present invention also offers carbon material for lithium ion battery cathode prepared by a kind of any of the above-described method.
Cathode of lithium battery material with carbon element prepared by the present invention, has good electric conductivity, cyclical stability, and when lithium ion battery, capacity is high, and service life is long.
Detailed description of the invention
Embodiment one
Pretreating graphite
By in the concentrated sulfuric acid solution immersing rapidly less than 10 DEG C after graphite heating to 100 DEG C, add surfactant sonic oscillation, make the fully oxidized separation of graphite, then product is reduced, i.e. form the mono-layer graphite of high yield, then by powder body graphite that mono-layer graphite ball mill pulverizing to particle diameter is 5 μm.
Remove the impurity in graphite
Powder body graphite is processed 2 hours in 500 DEG C in the sodium hydroxide solution that concentration is 50%, then carries out pickling in the sulfuric acid solution that concentration is 50%, then wash and be dried, to remove the impurity in powder body graphite.
Graphite composite powder after going the removal of impurity is modified
Graphite composite powder is mixed homogeneously with the nickel oxide accounting for graphite quality 4%, put in carbide furnace, the programming rate of carbide furnace is set as 100 DEG C/h begin to warm up, stop when reaching 1100 DEG C heating up, keep 6 hours at such a temperature, then in 1500 DEG C of catalyzed graphitization 1 hours under a nitrogen, modified powder graphite is obtained.
Modified graphite powder body is carried out reduction treatment
Under the atmosphere of CO (carbon monoxide converter) gas, in 500-700 DEG C, modified powder graphite is carried out surface reduction and process 2 hours.
Graphite composite powder after reduction treatment is carried out thin film process
Using chemical vapour deposition technique, with ethane as carbon source, depositing temperature is 700 DEG C, sedimentation time is 2 hours, graphite composite powder after reduction treatment is carried out peplos so that it is Surface coating last layer thickness be the carbon of 1 μm to improve initial coulomb efficiency, i.e. prepare lithium-ion electric negative pole pond material with carbon element.
Embodiment two
Pretreating graphite
By in the concentrated nitric acid solution immersing rapidly less than 10 DEG C after graphite heating to 300 DEG C, add surfactant sonic oscillation, make the fully oxidized separation of graphite, then product is reduced, i.e. form the mono-layer graphite of high yield, then by powder body graphite that mono-layer graphite ball mill pulverizing to particle diameter is 10 μm.
Remove the impurity in graphite
Powder body graphite is processed 4 hours in 550 DEG C in the sodium hydroxide solution that concentration is 70%, then carries out pickling in the sulfuric acid solution that concentration is 60%, then wash and be dried, to remove the impurity in powder body graphite.
Graphite composite powder after going the removal of impurity is modified
Graphite composite powder is mixed homogeneously with the nickel oxide accounting for graphite quality 6%, put in carbide furnace, the programming rate of carbide furnace is set as 100 DEG C/h begin to warm up, stop when reaching 1100 DEG C heating up, keep 6 hours at such a temperature, then in 1700 DEG C of catalyzed graphitization 2 hours under a nitrogen, modified powder graphite is obtained.
Modified graphite powder body is carried out reduction treatment
Under the atmosphere of CO (carbon monoxide converter) gas, in 700 DEG C, modified powder graphite is carried out surface reduction and process 4 hours.
Graphite composite powder after reduction treatment is carried out thin film process
Using chemical vapour deposition technique, with ethane as carbon source, depositing temperature is 900 DEG C, sedimentation time is 4 hours, graphite composite powder after reduction treatment is carried out peplos so that it is Surface coating last layer thickness be the carbon of 2 μm to improve initial coulomb efficiency, i.e. prepare lithium-ion electric negative pole pond material with carbon element.
Comparative example
Graphite is directly ground to the powder of 10 μm particle diameters, standby.
The lithium ion battery negative pole carbon material being respectively adopted embodiment one, two and comparative example makes the negative plate of same size, then makes battery, and electrolyte is 1.5mol/L LiPF6EC(ethyl carbonate ester)+DMC(dimethyl carbonate) (volume ratio 1: 1) solution, and be circulated performance test under conditions of constant current 0.1C.This embodiment one with two material compared with the material of comparative example, first discharge specific capacity improves more than 40-50%, and cycle life improves more than 1 times.
Claims (4)
1. the preparation method of a carbon material for lithium ion battery cathode, it is characterised in that comprise the steps:
Step 1, pretreating graphite
By in the concentrated sulphuric acid or the concentrated nitric acid solution that immerse rapidly less than 10 DEG C after graphite heating to 100-300 DEG C,
Add surfactant sonic oscillation, make the fully oxidized separation of graphite, then product is reduced, i.e. form high yield
Mono-layer graphite, then by powder body graphite that mono-layer graphite ball mill pulverizing to particle diameter is 5-10 μm；
Step 2, removes the impurity in graphite
Powder body graphite is processed 2-4 hour in the sodium hydroxide solution that concentration is 50-70% in 500-550 DEG C,
In the sulfuric acid solution that concentration is 50-60%, carry out pickling again, then wash and be dried, to remove powder body graphite
In impurity；
Step 3, is modified the graphite composite powder after going the removal of impurity
Graphite composite powder is mixed homogeneously with the nickel oxide accounting for graphite quality 4-6%, puts in carbide furnace, by carbonization
The programming rate of stove is set as 100 DEG C/h and begins to warm up, and stops when reaching 1100 DEG C heating up, at this
At a temperature of keep 6 hours, then in 1500-1700 DEG C of catalyzed graphitization 1-2 hour under a nitrogen, changed
Property powder body graphite；
Step 4, carries out reduction treatment to modified graphite powder body
Under the atmosphere of CO (carbon monoxide converter) gas, at 500-700 DEG C, modified powder body graphite is carried out surface also
Original place is managed 2-4 hour；
Step 5, carries out thin film process to the graphite composite powder after reduction treatment
Use chemical vapour deposition technique, the graphite composite powder after reduction treatment is carried out peplos so that it is on Surface coating
A layer thickness be the carbon of 1-2 μm to improve initial coulomb efficiency, i.e. prepare carbon material for lithium ion battery cathode,
Wherein chemical vapor deposition conditions: carbon source is the alkane of C1～C5, depositing temperature is 700-900 DEG C, deposition
Time is 2-4 hour.
Method the most according to claim 1, it is characterised in that carbon source described in step 5 is C1's～C3
Alkane.
Method the most according to claim 2, it is characterised in that carbon source described in step 5 is ethane.
4. the carbon material for lithium ion battery cathode that prepared by a method as claimed in claim 1.
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| CN111463438A (en) * | 2019-01-18 | 2020-07-28 | 中国科学院上海硅酸盐研究所 | Typha carbon lithium air battery positive electrode material and preparation method and application thereof |
| CN111439748B (en) * | 2020-03-12 | 2021-12-03 | 深圳市德方纳米科技股份有限公司 | Regenerated graphite material and preparation method thereof |
| EP3986833A4 (en) | 2020-05-18 | 2022-11-02 | Ecograf Limited | Method of producing purified graphite |
| CN111792640B (en) * | 2020-07-31 | 2022-05-06 | 广东凯金新能源科技股份有限公司 | Spherical low-expansion high-capacity graphite anode material, preparation method and lithium ion battery |
| CN112234171B (en) * | 2020-09-08 | 2022-04-08 | 中南大学 | Silicon-natural graphite composite material, application thereof and method for preparing silicon-natural graphite composite material by catalyzing with trace harmless impurities |
| CN112875697A (en) * | 2021-02-02 | 2021-06-01 | 广东凯金新能源科技股份有限公司 | High-energy-density low-temperature quick-charging artificial graphite material and preparation method thereof |
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| US5908715A (en) * | 1997-05-30 | 1999-06-01 | Hughes Electronics Corporation | Composite carbon materials for lithium ion batteries, and method of producing same |
| CN101320821A (en) * | 2007-06-04 | 2008-12-10 | 中南大学 | An energy storage device having both the characteristics of a capacitor and a lithium-ion battery and a manufacturing method thereof |
| CN101630737A (en) * | 2009-08-19 | 2010-01-20 | 河北理工大学 | Method for preparing tin-nickel alloy of cathode materials of lithium ion battery by electrolyzing melted salt |
| CN102544500A (en) * | 2012-03-22 | 2012-07-04 | 上海锦众信息科技有限公司 | Lithium ion battery cathode material and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5908715A (en) * | 1997-05-30 | 1999-06-01 | Hughes Electronics Corporation | Composite carbon materials for lithium ion batteries, and method of producing same |
| CN101320821A (en) * | 2007-06-04 | 2008-12-10 | 中南大学 | An energy storage device having both the characteristics of a capacitor and a lithium-ion battery and a manufacturing method thereof |
| CN101630737A (en) * | 2009-08-19 | 2010-01-20 | 河北理工大学 | Method for preparing tin-nickel alloy of cathode materials of lithium ion battery by electrolyzing melted salt |
| CN102544500A (en) * | 2012-03-22 | 2012-07-04 | 上海锦众信息科技有限公司 | Lithium ion battery cathode material and preparation method thereof |
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