CN104934571A - Preparation method of ternary cathode material coated with Co and Ti through ball milling - Google Patents
Preparation method of ternary cathode material coated with Co and Ti through ball milling Download PDFInfo
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- CN104934571A CN104934571A CN201510072232.2A CN201510072232A CN104934571A CN 104934571 A CN104934571 A CN 104934571A CN 201510072232 A CN201510072232 A CN 201510072232A CN 104934571 A CN104934571 A CN 104934571A
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- cathode material
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- sintering
- lithium carbonate
- tertiary cathode
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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 invention relates to preparation of cathode material for a lithium ion battery and specifically to a preparation method of a ternary cathode material coated with Co and Ti through ball milling. The method comprises the steps as follows: step 1, performing three-dimensional mechanical mixing to a 523-type ternary precursor and battery-grade lithium carbonate, then sintering the mixture in an air sintering furnace at the temperature of 600 to 700 degrees centigrade, grinding and crushing the obtained product after cooling to obtain a 523-type ternary cathode material; step 2, mixing the 523-type ternary cathode material with cobaltous oxide, the battery-grade lithium carbonate and an analytically pure-grade TiO2 additive in a high-energy ball-milling machine; taking the mixed sample out and using distilled water to clean the sample; sintering the cleaned sample, taking the sintered sample out and grinding the sample to obtain a finished product. The preparation method of the invention could be used for performing LiCoO2 coating to a surface of the ternary material and using the Ti to modify LiCoO2 part so as to effectively improve capacity retention ratio of ternary cathode material while being recycled for many times.
Description
Technical field
The present invention relates to the preparation of anode material for lithium-ion batteries, specifically the preparation method of the tertiary cathode material of a kind of ball milling coated Co, Ti.
Background technology
Anode material for lithium ion battery the most ripe is in the market LiCoO
2, have that compacting is high, good processability energy feature, but it is expensive, the space of improving performance is further very little; And 523 type LiNi
0.5co
0.2mn
0.3o
2tertiary cathode material has the features such as price is low, specific discharge capacity is high, stable circulation, but common 523 tertiary cathode materials repeatedly in cyclic process capability retention lower, have impact on the further raising of its performance.
Summary of the invention
Technical problem to be solved by this invention is, provides a kind of preparation method that can improve the tertiary cathode material repeatedly tertiary cathode material of ball milling coated Co, Ti of circulation volume conservation rate.
Preparation method of the present invention comprises the following steps:
Step one, by granularity D50 be 523 type ternary precursors of 10 μm of levels with battery-level lithium carbonate with precursor: the ratio of lithium carbonate=1:1.2 is carried out three-dimensional machinery and is mixed, batch mixing ball weight: weight of material=1.5:1, then in the sintering furnace of blowing air 600-700 DEG C carry out sintering 10 hours, carry out grinding after cooling broken, obtain 523 tertiary cathode materials;
523 tertiary cathode materials and granularity D50 are cobalt oxide, battery-level lithium carbonate, the pure level TiO of analysis of 5 μm of levels by step 2
2additive mixes in high energy ball mill, and mixed proportion is 523 tertiary cathode materials: cobalt oxide: lithium carbonate: TiO
2=100:1:1.1:5 × 10
-4, batch mixing ball weight: weight of material=1:2, biased sample taking-up distilled water is cleaned, in 900-1000 DEG C of air atmosphere, sinter 10 hours, and after sintering, sample takes out grinding, obtains finished product.
Preferably, in described step one, sintering temperature is 650 DEG C, and in step 2, sintering temperature is 950 DEG C.
The present invention is by precursor---cobalt oxide, lithium carbonate and the additive Ti source---TiO by 523 ternary materials of routine and cobalt acid lithium
2, mixed by high energy ball mill, make it carry out and reaction, then at high temperature heat-treat, obtain high performance blended anode material, have good first discharge specific capacity and good circulation conservation rate; Can effectively avoid simple mechanical three-dimensional to mix caused element with the stage of reaction penetrating many, affect the structure of 523 type element matrixes and cause the defect that the coated degree of material surface is inadequate wherein during high-energy ball milling.LiCoO is carried out on ternary material surface
2coated, composite material not only can be allowed to show the high specific discharge capacity of ternary material, cheap advantage, specific area and the pH of material can also be reduced, reduce the interfacial reaction that occurs with electrolyte in cell reaction of material, use the coated of Ti then can to the LiCoO on composite material surface
2part carries out modification, reduces LiCoO
2the reaction of pure material and electrolyte.
Embodiment
The method of the embodiment of the present invention comprises the following steps:
Step one, by granularity D50 be 523 type ternary precursors of 10 μm of levels with battery-level lithium carbonate with precursor: the ratio of lithium carbonate=1:1.2 is carried out simple three-dimensional machinery and is mixed 4 hours, batch mixing ball weight: weight of material=1.5:1, then in the sintering furnace of blowing air 650 DEG C carry out sintering 10 hours, throughput is 40L/min.Carry out grinding after cooling broken, obtain 523 tertiary cathode materials;
Sample one and granularity D50 are cobalt oxide, battery-level lithium carbonate, the pure level TiO of analysis of 5 μm of levels by step 2
2additive mixes in high energy ball mill, and mixed proportion is sample one: cobalt oxide: lithium carbonate: TiO
2=100:1:1.1:5 × 10
-4, batch mixing ball weight: weight of material=1:2, uses alcohol to carry out ball milling 4 hours by noting in ball grinder to 4/5 place, and biased sample taking-up distilled water is cleaned, in 950 DEG C of air atmospheres, sinter 10 hours, and after sintering, sample takes out grinding, obtains finished product.
After testing, result is as follows for the positive electrode that the embodiment of the present invention obtains:
1, particle D50 size is at 11-15 μm, specific area < 0.3m
2/ g;
2,0.2C first capacity be greater than 160mAh/g;
3, capability retention > 90% after 500 circulations.
Claims (2)
1. a preparation method for the tertiary cathode material of ball milling coated Co, Ti, is characterized in that: comprise the following steps,
Step one, by granularity D50 be 523 type ternary precursors of 10 μm of levels with battery-level lithium carbonate with precursor: the ratio of lithium carbonate=1:1.2 is carried out three-dimensional machinery and is mixed, batch mixing ball weight: weight of material=1.5:1, then in the sintering furnace of blowing air 600-700 DEG C carry out sintering 10 hours, carry out grinding after cooling broken, obtain 523 tertiary cathode materials;
523 tertiary cathode materials and granularity D50 are cobalt oxide, battery-level lithium carbonate, the pure level TiO of analysis of 5 μm of levels by step 2
2additive mixes in high energy ball mill, and mixed proportion is 523 tertiary cathode materials: cobalt oxide: lithium carbonate: TiO
2=100:1:1.1:5 × 10
-4, batch mixing ball weight: weight of material=1:2, biased sample taking-up distilled water is cleaned, in 900-1000 DEG C of air atmosphere, sinter 10 hours, and after sintering, sample takes out grinding, obtains finished product.
2. the preparation method of the tertiary cathode material of ball milling according to claim 1 coated Co, Ti, is characterized in that: in step one, sintering temperature is 650 DEG C, in step 2, sintering temperature is 950 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510072232.2A CN104934571A (en) | 2015-02-11 | 2015-02-11 | Preparation method of ternary cathode material coated with Co and Ti through ball milling |
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|---|---|---|---|
| CN201510072232.2A CN104934571A (en) | 2015-02-11 | 2015-02-11 | Preparation method of ternary cathode material coated with Co and Ti through ball milling |
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| CN104934571A true CN104934571A (en) | 2015-09-23 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107215903A (en) * | 2017-06-07 | 2017-09-29 | 四川科能锂电有限公司 | The preparation method of high voltage tertiary cathode material |
| WO2023165626A1 (en) * | 2022-03-02 | 2023-09-07 | 巴斯夫杉杉电池材料有限公司 | Ternary positive electrode material for lithium-ion battery and preparation method therefor |
| WO2023165160A1 (en) * | 2022-03-02 | 2023-09-07 | 广东邦普循环科技有限公司 | Positive electrode material, and preparation method therefor and use thereof |
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| CN102237518A (en) * | 2010-05-07 | 2011-11-09 | 深圳市比克电池有限公司 | Treatment method for ternary material and method for improving capacity and cycle performance of lithium battery |
| CN103500827A (en) * | 2013-10-11 | 2014-01-08 | 宁德新能源科技有限公司 | Lithium ion battery and multi-element positive material thereof as well as preparation method of multi-element positive material |
| CN103618081A (en) * | 2013-11-22 | 2014-03-05 | 南通瑞翔新材料有限公司 | High-voltage high-capacity anode material for lithium ion battery and preparation method of anode material |
| CN103985857A (en) * | 2014-05-19 | 2014-08-13 | 青岛乾运高科新材料股份有限公司 | Mixed lithium battery positive material and preparation method thereof |
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2015
- 2015-02-11 CN CN201510072232.2A patent/CN104934571A/en active Pending
Patent Citations (4)
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| CN102237518A (en) * | 2010-05-07 | 2011-11-09 | 深圳市比克电池有限公司 | Treatment method for ternary material and method for improving capacity and cycle performance of lithium battery |
| CN103500827A (en) * | 2013-10-11 | 2014-01-08 | 宁德新能源科技有限公司 | Lithium ion battery and multi-element positive material thereof as well as preparation method of multi-element positive material |
| CN103618081A (en) * | 2013-11-22 | 2014-03-05 | 南通瑞翔新材料有限公司 | High-voltage high-capacity anode material for lithium ion battery and preparation method of anode material |
| CN103985857A (en) * | 2014-05-19 | 2014-08-13 | 青岛乾运高科新材料股份有限公司 | Mixed lithium battery positive material and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107215903A (en) * | 2017-06-07 | 2017-09-29 | 四川科能锂电有限公司 | The preparation method of high voltage tertiary cathode material |
| WO2023165626A1 (en) * | 2022-03-02 | 2023-09-07 | 巴斯夫杉杉电池材料有限公司 | Ternary positive electrode material for lithium-ion battery and preparation method therefor |
| WO2023165160A1 (en) * | 2022-03-02 | 2023-09-07 | 广东邦普循环科技有限公司 | Positive electrode material, and preparation method therefor and use thereof |
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| C06 | Publication | ||
| PB01 | Publication | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20151117 Address after: 753000, room 323, Xinghai town office building, Dawukou District, the Ningxia Hui Autonomous Region, Shizuishan Applicant after: JIANGSU KING LITHIUM CELL CO., LTD. Address before: Jinyang Jingkou Industrial Park Road 212006 Zhenjiang City, Jiangsu province Jingkou District No. 9 Applicant before: Jiangsu King Lithium Cell Co.,Ltd. |
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| RJ01 | Rejection of invention patent application after publication | ||
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Application publication date: 20150923 |