CN102709542B - Method for repairing oxygen defect in preparation process of spinel lithium manganate as lithium-ion cathode material - Google Patents
Method for repairing oxygen defect in preparation process of spinel lithium manganate as lithium-ion cathode material Download PDFInfo
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Abstract
The invention discloses a method for repairing oxygen defect in a preparation process of spinel lithium manganate as a lithium-ion cathode material. The method comprises the following steps: (1) taking lithium carbonate and electrolytic manganese dioxide as main reaction substances and doping with aluminium hydroxide; (2) weighing reactants in proportion and putting the reactants in a horizontal-type ball mill tank for coarsely mixing; (3) putting the coarsely mixed materials into an automatic granulator for finely mixing and directly granulating the materials in the granulator after finely mixing; (4) putting the granulated materials in a drying oven for drying and putting the dried granulated materials into an atmosphere furnace for calcining for the first time; and (5) smashing the calcined materials, supplementing the lithium and carrying out secondary calcining. With the adoption of the method, the material performance is improved; and the preparation process is simple and easy in operation; the raw materials are easily available; and the obtained product is uniform.
Description
Technical field
The present invention relates to anode material for lithium-ion batteries technical field, be specifically related to the restorative procedure of oxygen defect in lithium ion anode material lithium manganate having spinel structure preparation process.
Background technology
Lithium manganese oxide is acknowledged as for electric automobile or hybrid-electric car power supply one of the most promising lithium ion secondary battery anode material because of features such as manganese aboundresources, cheap, environmental friendliness and fail safe height.Lithium manganese oxide is that capacity attenuation is comparatively serious as the disadvantage of lithium ion secondary battery anode material, the main cause of its capacity attenuation is: in charge and discharge process, there is Jahn-Teller effect, Mn in electrolyte, dissolve and structure in the oxygen defect that exists.
At present, by doping yin, yang ion, carry out stable spinel structure and improve the existing a large amount of research of its chemical property, but to the correlative study of material self structure defect seldom.In order more to understand the impact of oxygen defect on material property in depth, and how to repair this defect.
Summary of the invention
The deficiency existing for prior art, technical problem to be solved by this invention is, provide a kind of can repair materials in oxygen defect, reduce capacity attenuation, improve the restorative procedure of oxygen defect in the lithium ion anode material lithium manganate having spinel structure preparation process of material electrochemical performance.
For solving the problems of the technologies described above, the technical solution used in the present invention is: the restorative procedure of oxygen defect in a kind of lithium ion anode material lithium manganate having spinel structure preparation process, comprises the following steps:
(1), to take lithium carbonate and electrolytic manganese dioxide be key reaction material, doped with hydrogen aluminium oxide;
(2), according to proportioning, weigh each reactant, put into horizontal ball grinder slightly mixed;
(3), that the material after slightly mixed is put into automatic granulator is carefully mixed, after thin mixed end, directly in comminutor, carries out granulation;
(4), that granulation material is put into baking oven is dry, after to be dried completing, put into atmosphere furnace and once calcine;
(5), the material solution after calcining once is broken, carry out after the supplementing of lithium secondary clacining.
In above-mentioned lithium ion anode material lithium manganate having spinel structure preparation process, each reactant quality proportioning of the restorative procedure of oxygen defect is 728: 101: 3192.
The restorative procedure of oxygen defect in above-mentioned lithium ion anode material lithium manganate having spinel structure preparation process, organizing the mixed time is 0.5h, carefully mixes as 20min.
The restorative procedure of oxygen defect in above-mentioned lithium ion anode material lithium manganate having spinel structure preparation process, granulation is to make adhesive with 5% or 3% polyvinyl alcohol (PVA), moisture 10%-20% in material, baking temperature is 150 ℃.
The restorative procedure of oxygen defect in above-mentioned lithium ion anode material lithium manganate having spinel structure preparation process, carry out secondary clacining, once calcining refers to that 1h is warming up to 350 ℃ from room temperature, at this temperature, be incubated 4h, 1h rises to 950 ℃ of insulation 5h again, then 2h is down to 650 ℃ of insulation 15h, last cooling naturally; Secondary clacining be 2h rise to 650 ℃ insulation 26h naturally lower the temperature.
In lithium ion anode material lithium manganate having spinel structure preparation process of the present invention, the advantage of the restorative procedure of oxygen defect is: granulation processing had been carried out in invention before sintering to material,
Accompanying drawing explanation
Fig. 1 is the SEM figure of spinel structure LiMn2O4;
Fig. 2 is the XRD figure of the LiMn2O4 of spinel structure;
Fig. 3 is the lithium manganate battery cycle characteristics curve chart of spinel structure;
Fig. 4 is the first charge-discharge curve chart of the LiMn2O4 of spinel structure.
Embodiment
Below in conjunction with drawings and the specific embodiments, the present invention is described in further details;
Embodiment 1:
(1) weigh 693g lithium carbonate 101g aluminium hydroxide 3192g electrolytic manganese dioxide and put into the slightly mixed 30min of horizontal ball grinder.
(2) screen out zirconium ball, put into the carefully mixed 20min of automatic granulator.
(3) after thin mixed end, directly in comminutor, add 5%PVA to carry out granulation, in material, moisture 13%.
(4) after granulation dry materials, pouring material alms bowl into puts into atmosphere furnace and once calcines.
(5) after once sintered completing, particle solution is broken, add lithium carbonate 35g, mix and carry out secondary clacining, obtain final powder product.
(6) powder is done to XRD, SEM and Electrical Analysis test, result as Figure 1-Figure 4.
Embodiment 2:
(1) weigh 693g lithium carbonate 101g aluminium hydroxide 3192g electrolytic manganese dioxide and put into the slightly mixed 30min of horizontal ball grinder.
(2) screen out zirconium ball, put into the carefully mixed 20min of automatic granulator.
(3) after thin mixed end, directly in comminutor, add 3%PVA to carry out granulation, in material, moisture 16%.
(4) after granulation dry materials, pouring material alms bowl into puts into atmosphere furnace and once calcines.
(5) after once sintered completing, particle solution is broken, add lithium carbonate 35g, mix and carry out secondary clacining, obtain final powder product.
(6) product is tested.
Embodiment 3:
(1) weigh 728g lithium carbonate 101g aluminium hydroxide 3192g electrolytic manganese dioxide and put into the slightly mixed 30min of horizontal ball grinder.
(2) screen out zirconium ball, put into the carefully mixed 20min of automatic granulator.
(3) after thin mixed end, directly in comminutor, add 5%PVA to carry out granulation, in material, moisture 13%.
(4) after granulation dry materials, pouring material alms bowl into puts into atmosphere furnace and once calcines.
(5) after once sintered completing, particle solution is broken, carry out secondary clacining, obtain final powder product.
(6) powder is done to analytical test.
Certainly, above-mentioned explanation is not limitation of the present invention, and the present invention is also not limited to above-mentioned giving an example; those skilled in the art; in essential scope of the present invention, the variation of making, remodeling, interpolation or replacement, all should belong to protection scope of the present invention.
Claims (3)
1. a restorative procedure for oxygen defect in lithium ion anode material lithium manganate having spinel structure preparation process, is characterized in that, comprises the following steps:
(1), to take lithium carbonate and electrolytic manganese dioxide be key reaction material, doped with hydrogen aluminium oxide;
(2), according to proportioning, weigh each reactant, put into horizontal ball grinder slightly mixed;
(3), that the material after slightly mixed is put into automatic granulator is carefully mixed, after thin mixed end, directly in comminutor, carries out granulation;
(4), that granulation material is put into baking oven is dry, after to be dried completing, put into atmosphere furnace and once calcine;
(5), the material solution after calcining once is broken, carry out after the supplementing of lithium secondary clacining;
Wherein, the quality proportioning of lithium carbonate, aluminium hydroxide and electrolytic manganese dioxide is 728: 101: 3192, and once calcining refers to that 1h is warming up to 350 ℃ from room temperature, at this temperature, be incubated 4h, 1h rises to 950 ℃ of insulation 5h again, and then 2h is down to 650 ℃ of insulation 15h, last cooling naturally; Secondary clacining be 2h rise to 650 ℃ insulation 26h naturally lower the temperature.
2. the restorative procedure of oxygen defect in lithium ion anode material lithium manganate having spinel structure preparation process according to claim 1, is characterized in that: carrying out the thick mixed time is 0.5h, carefully mixes as 20min.
3. the restorative procedure of oxygen defect in lithium ion anode material lithium manganate having spinel structure preparation process according to claim 1, it is characterized in that: granulation is to make adhesive with 5% or 3% polyvinyl alcohol, moisture 10%-20% in material, baking temperature is 150 ℃.
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| CN103531775A (en) * | 2013-09-13 | 2014-01-22 | 东莞市天楠光电科技有限公司 | Preparation method of doped lithium-rich lithium manganese oxide cathode material |
| CN103808860B (en) * | 2014-02-21 | 2015-07-29 | 合肥国轩高科动力能源股份公司 | A kind of lithium ion anode material lithium defect inspection method |
| CN106532169A (en) * | 2016-12-16 | 2017-03-22 | 无锡晶石新型能源有限公司 | Method of recycling lithium manganate dust |
| CN110504414B (en) * | 2018-05-16 | 2022-07-05 | 中国科学院苏州纳米技术与纳米仿生研究所 | Defect metal oxide/porous nano carbon composite material and preparation method and application thereof |
| CN111509219B (en) * | 2020-04-13 | 2022-04-15 | 江门市科恒实业股份有限公司 | Lithium manganate battery material and preparation method thereof |
| CN111960467B (en) * | 2020-08-27 | 2022-12-27 | 长沙矿冶研究院有限责任公司 | Preparation process of multi-element material |
| CN117164011B (en) * | 2023-11-03 | 2024-04-12 | 宁德时代新能源科技股份有限公司 | Lithium manganate material, preparation method thereof, secondary battery and power utilization device |
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| CN1872702A (en) * | 2006-06-16 | 2006-12-06 | 南京航空航天大学 | Method for preparing spinel type lithium manganate in use for material of positive pole in lithium ion battery |
| CN101070191A (en) * | 2006-05-08 | 2007-11-14 | 上海川那电池制造有限公司 | Process for preparing lithium ion cell positive pole material |
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| CN101070191A (en) * | 2006-05-08 | 2007-11-14 | 上海川那电池制造有限公司 | Process for preparing lithium ion cell positive pole material |
| CN1872702A (en) * | 2006-06-16 | 2006-12-06 | 南京航空航天大学 | Method for preparing spinel type lithium manganate in use for material of positive pole in lithium ion battery |
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Denomination of invention: Method for repairing oxygen defect in preparation process of spinel lithium manganate as lithium-ion cathode material Effective date of registration: 20200629 Granted publication date: 20141105 Pledgee: China Construction Bank Corporation Qingdao Zhongshan Road sub branch Pledgor: QINGDAO QIANYUN HIGH-TECH NEW MATERIAL Co.,Ltd. Registration number: Y2020370010025 |
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