CN104701532A - Preparation method of lithium cobaltate positive material coated with nanometer aluminum oxide solid phase - Google Patents
Preparation method of lithium cobaltate positive material coated with nanometer aluminum oxide solid phase Download PDFInfo
- Publication number
- CN104701532A CN104701532A CN201510072191.7A CN201510072191A CN104701532A CN 104701532 A CN104701532 A CN 104701532A CN 201510072191 A CN201510072191 A CN 201510072191A CN 104701532 A CN104701532 A CN 104701532A
- Authority
- CN
- China
- Prior art keywords
- lithium cobaltate
- solid phase
- preparation
- lithium
- oxide solid
- 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.)
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 30
- 239000000463 material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000007790 solid phase Substances 0.000 title claims abstract description 17
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 title abstract 5
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000498 ball milling Methods 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims abstract description 4
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims abstract description 4
- 239000001095 magnesium carbonate Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 44
- 239000010941 cobalt Substances 0.000 claims description 13
- 229910017052 cobalt Inorganic materials 0.000 claims description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- 239000010406 cathode material Substances 0.000 claims description 10
- 239000002105 nanoparticle Substances 0.000 claims description 4
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 claims description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 abstract 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000000227 grinding Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 239000010405 anode material Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
Classifications
-
- 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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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to preparation of positive material for lithium ion batteries, and in particular relates to a preparation method of lithium cobaltate positive material coated with nanometer aluminum oxide solid phase. The method comprises the following steps: 1, preparing lithium cobaltate, namely, mixing tricobalt tetroxide with lithium carbonate, feeding 1400-1500ppm of basic magnesium carbonate, sintering the mixture at the temperature of 950-980 DEG C, naturally cooling in a furnace, and crushing to obtain lithium cobaltate; and 2, enabling lithium cobaltate to be coated with the nanometer aluminum oxide solid phase, namely, firstly feeding lithium cobaltate and nanometer aluminum oxide powder having the particle size D50 of 20-22nm into a ball mill, feeding grinding balls with the mass twice that of the material, sintering the material treated by ball-milling at the temperature of 780-800 DEG C, then naturally cooling in the furnace, and crushing the cooled material in a crusher to obtain the lithium cobaltate positive material coated with the nanometer aluminum oxide solid phase. After the preparation method is adopted, the cycle performance and the high-temperature performance of the lithium cobaltate positive material can be effectively improved, the coating uniformity of the lithium cobaltate positive material is good, and the product performance is stable.
Description
Technical field
The present invention relates to the preparation of anode material for lithium-ion batteries, specifically the preparation method of the coated lithium cobaltate cathode material of a kind of nano aluminium oxide solid phase.
Background technology
Anode material for lithium ion battery the most ripe is at present cobalt acid lithium (LiCoO
2), it has, and compacting is high, the feature of good processability, but its cycle performance and high-temperature behavior still have deficiency.
Summary of the invention
Technical problem to be solved by this invention is, provides a kind of cycle performance and the high-temperature behavior that can improve cobalt acid lithium material, the preparation method of the coated uniform and stable coated lithium cobaltate cathode material of nano aluminium oxide solid phase of material modification.
The preparation method of the coated lithium cobaltate cathode material of nano aluminium oxide solid phase of the present invention comprises the following steps:
Step one, the preparation of cobalt acid lithium: cobaltosic oxide and lithium carbonate are added in three-dimensional hybrid equipment according to lithium cobalt mol ratio 1.05-1.08 and mixes, add the basic magnesium carbonate of 1400-1500ppm, after mixing, material is sintered at 950-980 DEG C, afterwards with stove cooling, more broken obtained granularity D50 is the cobalt acid lithium of 10-10.5 μm;
Step 2, nano aluminium oxide solid phase is coated: the Nano-sized Alumina Powder being first 20-22nm by the cobalt of above-mentioned preparation acid lithium and granularity D50 adds in the ball grinder of ball mill according to the mass ratio of 190-210:1, then the abrading-ball of twice quality of material is added, to take out after the rotating speed ball milling 2-3h of 240-260r/min; Material after ball milling is sintered at 780-800 DEG C, cools with stove afterwards; Cooled material crusher in crushing obtains the coated lithium cobaltate cathode material of nano aluminium oxide solid phase that granularity D50 is 10-10.5 μm.
The coated lithium cobaltate cathode material of nano aluminium oxide solid phase obtained by the inventive method effectively improves cycle performance and the high-temperature behavior of material, and its coated uniformity is good, and properties of product are stablized.
Embodiment
The embodiment of the inventive method is through following steps:
Step one, the preparation of cobalt acid lithium: cobaltosic oxide and lithium carbonate are added in three-dimensional hybrid equipment according to lithium cobalt mol ratio 1.06, and add the basic magnesium carbonate of 1500ppm, after 25Hz mixes 4 hours, material is loaded crucible, at 980 DEG C, sinters 10h with Muffle furnace, cool with stove afterwards, pour material into crusher in crushing 10s, obtained granularity D50 is the cobalt acid lithium of 10.5 μm;
Step 2, nano aluminium oxide solid phase is coated:
1, the Nano-sized Alumina Powder being first 20nm by the cobalt of above-mentioned preparation acid lithium and granularity D50 adds in the ball grinder of horizontal planetary ball mill according to the mass ratio of 200:1, then adds the abrading-ball of twice quality of material, to take out after the rotating speed ball milling 3h of 250r/min;
2, above-mentioned material is loaded crucible, at 800 DEG C, sinter 5h with Muffle furnace, cool with stove afterwards;
3, by above-mentioned material crusher in crushing 10s, obtained granularity D50 is the coated lithium cobaltate cathode material of nano aluminium oxide solid phase of 10 μm.
Detect product prepared by the embodiment of the present invention, result is as follows:
1, granularity D50 is 10 μm, and surface uniform is dispersed with nano alumina particles;
2, coated sample and not coated sample are made half-cell respectively, 3.00V is discharged to 0.5C after charging to 4.35V, the specific discharge capacity of coated, not coated cobalt acid is respectively 167.6mAh/g and 170.9mAh/g, because coated rear product cobalt content reduces, so capacity slightly declines;
3, coated sample is respectively 96.4% with capability retention after 1C discharge cycles 200 times at normal temperature 25 DEG C, and not coated sample is 94.9%, and cycle performance significantly improves;
4, after storing 48h at 55 DEG C, coated sample, capability retention is 96.0%, and internal resistance rate of change is 9.8%, and not coated sample is 90.4% and 19.9%, and the high-temperature behavior of battery significantly improves.
Claims (2)
1. a preparation method for the coated lithium cobaltate cathode material of nano aluminium oxide solid phase, is characterized in that: comprise the following steps,
Step one, the preparation of cobalt acid lithium: cobaltosic oxide and lithium carbonate are added in three-dimensional hybrid equipment according to lithium cobalt mol ratio 1.05-1.08 and mixes, add the basic magnesium carbonate of 1400-1500ppm, after mixing, material is loaded crucible, sinter at 950-980 DEG C, afterwards with stove cooling, more broken obtained granularity D50 is the cobalt acid lithium of 10-10.5 μm;
Step 2, nano aluminium oxide solid phase is coated: the Nano-sized Alumina Powder being first 20-22nm by the cobalt of above-mentioned preparation acid lithium and granularity D50 adds in the ball grinder of ball mill according to the mass ratio of 190-210:1, then the abrading-ball of twice quality of material is added, to take out after the rotating speed ball milling 2-3h of 240-260 r/min; Material after ball milling is sintered at 780-800 DEG C, cools with stove afterwards; Cooled material crusher in crushing obtains the coated lithium cobaltate cathode material of nano aluminium oxide solid phase that granularity D50 is 10-10.5 μm.
2. the preparation method of the coated lithium cobaltate cathode material of nano aluminium oxide solid phase according to claim 1, is characterized in that: in step 2, the granularity D50 of Nano-sized Alumina Powder is 20nm.
Priority Applications (1)
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| CN201510072191.7A CN104701532A (en) | 2015-02-11 | 2015-02-11 | Preparation method of lithium cobaltate positive material coated with nanometer aluminum oxide solid phase |
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| CN201510072191.7A CN104701532A (en) | 2015-02-11 | 2015-02-11 | Preparation method of lithium cobaltate positive material coated with nanometer aluminum oxide solid phase |
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| CN104701532A true CN104701532A (en) | 2015-06-10 |
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|---|---|---|---|
| CN201510072191.7A Pending CN104701532A (en) | 2015-02-11 | 2015-02-11 | Preparation method of lithium cobaltate positive material coated with nanometer aluminum oxide solid phase |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105118989A (en) * | 2015-07-07 | 2015-12-02 | 湖南杉杉新材料有限公司 | Lithium ion battery lithium cobaltate positive electrode material and preparation method thereof |
| CN105428625A (en) * | 2015-12-09 | 2016-03-23 | 山东齐星新材料科技有限公司 | Method for preparing alumina coated lithium cobalt oxide lithium ion battery material by aluminum salt solution aftertreatment |
| CN106025214A (en) * | 2016-06-07 | 2016-10-12 | 山东齐星新材料科技有限公司 | Post-processing process for aluminium oxide-coated lithium cobalt oxide |
| CN106299351A (en) * | 2016-11-07 | 2017-01-04 | 珠海格力电器股份有限公司 | Positive electrode slurry, preparation method thereof and lithium ion battery |
| CN107644986A (en) * | 2017-08-22 | 2018-01-30 | 格林美（无锡）能源材料有限公司 | A kind of positive electrode of conducting polymer composite cladding cobalt acid lithium and preparation method thereof |
| CN108376781A (en) * | 2018-04-17 | 2018-08-07 | 天津巴莫科技股份有限公司 | A kind of lithium-ion-power cell silicon-carbon cathode material and preparation method thereof |
| CN108735526A (en) * | 2018-05-28 | 2018-11-02 | 浙江微创新能源有限公司 | Mend lithium material Li2NiO2Preparation method, use the Li2NiO2Lithium-ion capacitor |
| CN110190276A (en) * | 2019-07-10 | 2019-08-30 | 河南电池研究院有限公司 | A kind of preparation method of niobium, aluminium codope anode material for lithium-ion batteries |
| CN110672833A (en) * | 2018-07-02 | 2020-01-10 | 欧蒙医学实验诊断股份公司 | Coated solid phase chips and preparation thereof |
| CN113851617A (en) * | 2020-06-28 | 2021-12-28 | 天津国安盟固利新材料科技股份有限公司 | Double-metal-element co-coated lithium cobaltate material and preparation method thereof |
| CN114538527A (en) * | 2022-01-12 | 2022-05-27 | 北京泰丰先行新能源科技有限公司 | Lithium cobaltate positive electrode material with stable surface structure and preparation method thereof |
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| CN104037407A (en) * | 2014-05-22 | 2014-09-10 | 北大先行科技产业有限公司 | Lithium cobalt oxide compound material coated with lithium super-Ion conductor and preparation method thereof |
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| CN1731601A (en) * | 2005-06-15 | 2006-02-08 | 东莞新能源电子科技有限公司 | Method for improving secondary lithium ion battery cathode material safety performance |
| CN103236541A (en) * | 2013-04-12 | 2013-08-07 | 中信国安盟固利电源技术有限公司 | Method for improving storage performance of lithium cobalt oxide at high voltage and high temperature |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105118989A (en) * | 2015-07-07 | 2015-12-02 | 湖南杉杉新材料有限公司 | Lithium ion battery lithium cobaltate positive electrode material and preparation method thereof |
| CN105428625A (en) * | 2015-12-09 | 2016-03-23 | 山东齐星新材料科技有限公司 | Method for preparing alumina coated lithium cobalt oxide lithium ion battery material by aluminum salt solution aftertreatment |
| CN106025214B (en) * | 2016-06-07 | 2019-05-24 | 山东齐星新材料科技有限公司 | The aftertreatment technology of alumina-coated cobalt acid lithium |
| CN106025214A (en) * | 2016-06-07 | 2016-10-12 | 山东齐星新材料科技有限公司 | Post-processing process for aluminium oxide-coated lithium cobalt oxide |
| CN106299351B (en) * | 2016-11-07 | 2019-12-10 | 珠海格力电器股份有限公司 | positive electrode slurry, preparation method thereof and lithium ion battery |
| CN106299351A (en) * | 2016-11-07 | 2017-01-04 | 珠海格力电器股份有限公司 | Positive electrode slurry, preparation method thereof and lithium ion battery |
| CN107644986A (en) * | 2017-08-22 | 2018-01-30 | 格林美（无锡）能源材料有限公司 | A kind of positive electrode of conducting polymer composite cladding cobalt acid lithium and preparation method thereof |
| CN108376781A (en) * | 2018-04-17 | 2018-08-07 | 天津巴莫科技股份有限公司 | A kind of lithium-ion-power cell silicon-carbon cathode material and preparation method thereof |
| CN108735526A (en) * | 2018-05-28 | 2018-11-02 | 浙江微创新能源有限公司 | Mend lithium material Li2NiO2Preparation method, use the Li2NiO2Lithium-ion capacitor |
| CN110672833A (en) * | 2018-07-02 | 2020-01-10 | 欧蒙医学实验诊断股份公司 | Coated solid phase chips and preparation thereof |
| CN110190276A (en) * | 2019-07-10 | 2019-08-30 | 河南电池研究院有限公司 | A kind of preparation method of niobium, aluminium codope anode material for lithium-ion batteries |
| CN113851617A (en) * | 2020-06-28 | 2021-12-28 | 天津国安盟固利新材料科技股份有限公司 | Double-metal-element co-coated lithium cobaltate material and preparation method thereof |
| CN114538527A (en) * | 2022-01-12 | 2022-05-27 | 北京泰丰先行新能源科技有限公司 | Lithium cobaltate positive electrode material with stable surface structure and preparation method thereof |
| CN114538527B (en) * | 2022-01-12 | 2024-03-19 | 北京泰丰先行新能源科技有限公司 | Lithium cobaltate positive electrode material with stable surface structure and preparation method thereof |
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| Date | Code | Title | Description |
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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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Application publication date: 20150610 |