CN102169981B - Lithium cell cathode material with manganese-based laminated crystal structure and preparation method thereof - Google Patents
Lithium cell cathode material with manganese-based laminated crystal structure and preparation method thereof Download PDFInfo
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- CN102169981B CN102169981B CN2011100823344A CN201110082334A CN102169981B CN 102169981 B CN102169981 B CN 102169981B CN 2011100823344 A CN2011100823344 A CN 2011100823344A CN 201110082334 A CN201110082334 A CN 201110082334A CN 102169981 B CN102169981 B CN 102169981B
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- crystal structure
- powder
- saggar
- cathode material
- lithium
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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
Abstract
The invention relates to a manufacture technology of lithium cells, in particular to a preparation method of a lithium cell cathode material with a manganese-based laminated crystal structure, which comprises the steps of: 1, preparing a precursor of LI[Li0.20Ni0.133Co0.133Mn0.534]O2 by adopting a mechanical activating method; 2, pelleting by adopting a closed cycle spraying drying method; and 3, preparing a laminated crystal structure Li[Li0.20Ni0.133Co0.133Mn0.534]O2 by adopting a high-temperature solid phase method. In the material and the method, most of cobalt in lithium cobaltite is replaced with cheap metal manganese, cost of raw materials is lower, the preparation process is simple, and micron-level powder particles can show excellent cell properties. Through detection, capacity of the cathode material reaches 236mAh/g and is about 60 percent higher than that of lithium cobaltite and lithium iron phosphate, and the cathode material has excellent safety property.
Description
Technical field
The present invention relates to the lithium battery manufacturing technology, specifically a kind of lithium battery cathode material with manganese-based layered-crystal structure and preparation method thereof.
Background technology
Anode material of lithium battery commonly used mainly contains three kinds in the market: cobalt acid lithium (LiCoO
2), LiMn2O4 (LiMn
2O
4) and LiFePO4 (LiFePO
4).
Cobalt acid lithium (LiCoO
2) have layered crystal mechanism, the about 140mAh/g of accumulate capacity, the cycle performance comparative superiority, but because the expensive price of raw material cobalt, its application is confined to small-capacity cells, for example the rechargeable battery of small-sized electronic product.
LiMn2O4 (LiMn
2O
4), having spinel crystal structure, the cost of raw material is lower, but its capacity only has 100mAh/g, than cobalt acid lithium low about 30%.And its cycle performance can weaken greatly greater than (Electric power car operating temperature) under 50 ℃ the higher temperature, so preferred material that neither following Electric power car.
LiFePO4 (LiFePO
4) be a kind of iron-based positive electrode of just succeeding in developing recently, have olivine crystal structure, capacity is about 150mAh/g.Its cost of raw material is lower, but because its preparation technology is extremely complicated, final finished electrode material price is still higher.LiFePO4 is because the non-constant of its conductance, the powder particle that need to make Nano grade just can show reasonable cycle performance of battery, this is just to causing very large difficulty on the preparation technology, domestic have some producers attempting production, but unstable because of its batch quality, can not go into operation on a large scale always.At present only have in the world few manufacturer to can manufacture high performance LiFePO4,180,000 yuan/tons of prices very expensive (〉).
Summary of the invention
Technical problem to be solved by this invention is, provides that a kind of preparation technology is simple, material cost and low cost of manufacture, capacity is high, fail safe is good lithium battery cathode material with manganese-based layered-crystal structure and preparation method thereof.
Lithium battery cathode material with manganese-based layered-crystal structure of the present invention, its molecular formula is expressed as Li[Li
0.20Ni
0.133Co
0.133Mn
0.534] O
2, its cation mol ratio Li:Ni:Co:Mn=1.2:0.133:0.133:0.534.
The preparation method of positive electrode of the present invention is:
The first step, the standby Li[Li of mechanical activation legal system
0.20N
I0.133Co
0.133Mn
0.534] O
2Precursor, concrete steps are
1) with Li
2CO
3, Ni
2O
3, electrolysis MnO
2, Co
3O
4Take by weighing each raw material and mix by stoichiometric proportion, so that the cation mol ratio Li:Ni:Co:Mn=1.3:0.133:0.133:0.534 of raw material;
2) change the raw material that mix over to stirring ball mill and carry out mechanical activation, ratio of grinding media to material is 10:1, and rotating speed is 100r/min, and soak time is 3h;
Second step, the granulation of closed cycle spray drying process, concrete steps are
1) precursor that mechanical activation is prepared is by peristaltic pump input closed cycle spray dryer;
2) the spray dryer intake air temperature is 120-130 ℃, and the air outlet temperature is 65-75 ℃;
In the 3rd step, high temperature solid-state method prepares layered crystal structure Li[Li
0.20Ni
0.133Co
0.133Mn
0.534] O
2,
1) the resulting granulated powders of second step is contained in the saggar, again with the powder in the pressing plate pressure saggar, in the roller furnace that is placed on air atmosphere, 470-490 ℃ of heating 4-6 hour, naturally cools to 70-85 ℃ in the cooling zone of stove subsequently;
2) powder with cooling changes the ball mill ball milling over to, and ratio of grinding media to material is 10:1, and rotating speed is 100r/min, and Ball-milling Time is 1h;
3) powder behind the ball milling is contained in the saggar, presses powder in the saggar with pressing plate, subsequently in the roller furnace of air atmosphere 920-980 ℃ sintering 9-11 hour, sintering cools off naturally in the cooling zone of stove after finishing;
4) with the powder process jet mill grinding of cooling, obtain end product.
Material of the present invention and the more cheap manganese metal of method usefulness come the most cobalts in the substituting cobalt acid lithium, and the cost of raw material is lower, and preparation technology is simple, and the powder particle of micron level can show remarkable battery performance.After testing, the capacity of its positive electrode is up to 215mAh/g, than cobalt acid lithium and LiFePO4 from capacity high about about 40%.In the charging test, under the 1C discharge-rate, through 100 charging cycle, also possess more than 90% of initial capacity.And under super-large current (surpassing the 10C multiplying power) discharge scenario, experiment is caught fire and explosion phenomenon without any, proves the security performance that it is remarkable.This positive electrode will have boundless application prospect on the products such as hybrid vehicle.
Embodiment
Embodiment:
Adopt the mechanical activation method to prepare lithium battery cathode material with manganese-based layered-crystal structure Li[Li in conjunction with high temperature solid-state method
0.20Ni
0.133Co
0.133Mn
0.534] O
2, may further comprise the steps:
The first step, the standby Li[Li of mechanical activation legal system
0.20N
I0.133Co
0.133Mn
0.534] O
2Precursor, concrete steps are
1) with Li
2CO
3, Ni
2O
3, electrolysis MnO
2, Co
3O
4Take by weighing each raw material and mix by stoichiometric proportion, so that the cation mol ratio Li:Ni:Co:Mn=1.3:0.133:0.133:0.534 of raw material; Here Li
+: metal ion summation=1.25:0.8, greater than Li[Li
0.20Ni
0.133Co
0.133Mn
0.534] O
2In theoretical value (1.2:0.8), use excessive lithium, be because the sub-fraction lithium in sintering process, can vapor away.
2) input isopropyl alcohol (isopropyl alcohol is as dispersant) by peristaltic pump in stirring ball mill, change the raw material that mix over to stirring ball mill subsequently and carry out mechanical activation, ratio of grinding media to material is 10:1, and rotating speed is 100r/min, and soak time is 3h.Attention: the solid content of powder acetone mixed system is 18%;
Second step, the granulation of closed cycle spray drying process, concrete steps are
1) precursor that mechanical activation is prepared is by peristaltic pump input closed cycle spray dryer;
2) the spray dryer intake air temperature is 120-130 ℃, and the air outlet temperature is 65-75 ℃;
In the 3rd step, high temperature solid-state method prepares layered crystal structure Li[Li
0.20Ni
0.133Co
0.133Mn
0.534] O
2,
1) the resulting granulated powders of second step is contained in the saggar, again with the powder in the pressing plate pressure saggar, in the roller furnace that is placed on air atmosphere, 480 ℃ of heating 5 hours, naturally cools to 80 ℃ in the cooling zone of stove subsequently;
2) powder with cooling changes the ball mill ball milling over to, and ratio of grinding media to material is 10:1, and rotating speed is 100r/min, and Ball-milling Time is 1h;
3) powder behind the ball milling is contained in the saggar, presses powder in the saggar with pressing plate, 950 ℃ of sintering 10 hours in the roller furnace of air atmosphere subsequently, sintering cools off naturally in the cooling zone of stove after finishing;
4) with the powder process jet mill grinding of cooling, obtain end product.
The final products index is as follows:
Claims (1)
1. the preparation method of a lithium battery cathode material with manganese-based layered-crystal structure is characterized in that:
The first step, the standby Li[Li of mechanical activation legal system
0.20N
I0.133Co
0.133Mn
0.534] O
2Precursor, concrete steps are
1) with Li
2CO
3, NiCO
3, MnCO
3, Co
3O
4Take by weighing each raw material and mix by stoichiometric proportion, so that the cation mol ratio Li:Ni:Co:Mn=1.3:0.133:0.133:0.534 of raw material;
2) change the raw material that mix over to stirring ball mill and carry out mechanical activation, ratio of grinding media to material is 10:1, and rotating speed is 100r/min, and soak time is 3h;
Second step, the granulation of closed cycle spray drying process, concrete steps are
1) precursor that mechanical activation is prepared is by peristaltic pump input closed cycle spray dryer;
2) the spray dryer intake air temperature is 120-130 ℃, and the air outlet temperature is 65-75 ℃;
In the 3rd step, high temperature solid-state method prepares layered crystal structure Li[Li
0.20Ni
0.133Co
0.133Mn
0.534] O
2,
1) the resulting granulated powders of second step is contained in the saggar, again with the powder in the pressing plate pressure saggar, in the roller furnace that is placed on air atmosphere, 490-510 ℃ of heating 8-9 hour, naturally cools to 75-85 ℃ in the cooling zone of stove subsequently;
2) powder with cooling changes the ball mill ball milling over to, and ratio of grinding media to material is 10:1, and rotating speed is 100r/min, and Ball-milling Time is 1-2h;
3) powder behind the ball milling is contained in the saggar, presses powder in the saggar with pressing plate, subsequently in the roller furnace of air atmosphere 960-990 ℃ sintering 9-11 hour, sintering cools off naturally in the cooling zone of stove after finishing;
4) with the powder process jet mill grinding of cooling, obtain end product Li[Li
0.20Ni
0.133Co
0.133Mn
0.534] O
2
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100823344A CN102169981B (en) | 2011-04-02 | 2011-04-02 | Lithium cell cathode material with manganese-based laminated crystal structure and preparation method thereof |
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|---|---|---|---|
| CN2011100823344A CN102169981B (en) | 2011-04-02 | 2011-04-02 | Lithium cell cathode material with manganese-based laminated crystal structure and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN102169981A CN102169981A (en) | 2011-08-31 |
| CN102169981B true CN102169981B (en) | 2013-04-10 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102664268A (en) * | 2012-05-09 | 2012-09-12 | 北京好风光储能技术有限公司 | Composite electrode active particle and preparation method and application thereof |
| CN102881892B (en) * | 2012-10-15 | 2015-04-08 | 福建师范大学 | Method for preparing lithium-rich solid solution cathode material through oxidation/sintering |
| CN103972495B (en) * | 2014-05-16 | 2016-03-23 | 盐城市新能源化学储能与动力电源研究中心 | A kind of preparation method of lithium ion battery anode material nickel LiMn2O4 |
| CN108807897A (en) * | 2018-06-11 | 2018-11-13 | 四会市恒星智能科技有限公司 | Graphene anode material of lithium battery preparation method |
| CN109216688B (en) * | 2018-10-23 | 2021-09-17 | 桑顿新能源科技有限公司 | Ternary lithium battery material, preparation method thereof and lithium ion battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101740773A (en) * | 2009-12-22 | 2010-06-16 | 江苏环能通环保科技有限公司 | Lithium battery cathode material with manganese-based layered-crystal structure and preparation method thereof |
| CN101777643A (en) * | 2010-01-14 | 2010-07-14 | 镇江科捷锂电池有限公司 | Preparation method of anode material of Al2O3-cladding manganese-based laminated lithium battery |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101740773A (en) * | 2009-12-22 | 2010-06-16 | 江苏环能通环保科技有限公司 | Lithium battery cathode material with manganese-based layered-crystal structure and preparation method thereof |
| CN101777643A (en) * | 2010-01-14 | 2010-07-14 | 镇江科捷锂电池有限公司 | Preparation method of anode material of Al2O3-cladding manganese-based laminated lithium battery |
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| CN102169981A (en) | 2011-08-31 |
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Denomination of invention: Lithium battery cathode material with manganese-based layered-crystal structure and preparation method thereof Effective date of registration: 20130729 Granted publication date: 20130410 Pledgee: The Bank of Jiangsu Limited by Share Ltd Zhenjiang branch of science and technology Pledgor: Jiangsu King Lithium Cell Co.,Ltd. Registration number: 2013990000518 |
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Effective date of registration: 20180508 Address after: 753000 the Ningxia Hui Autonomous Region Shizuishan high tech Industrial Park, small and Medium Enterprises Incubator No. 9 workshop Patentee after: JIANGSU KING LITHIUM CELL CO., LTD. Address before: 212006 Jinyang Avenue, Jingkou Industrial Park, Zhenjiang, Jiangsu, 9 Patentee before: Jiangsu King Lithium Cell Co.,Ltd. |
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Granted publication date: 20130410 Termination date: 20190402 |
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