CN101764211B - Preparation method of spherical lithium manganese for lithium-ion battery cathode material - Google Patents
Preparation method of spherical lithium manganese for lithium-ion battery cathode material Download PDFInfo
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- CN101764211B CN101764211B CN200910019320A CN200910019320A CN101764211B CN 101764211 B CN101764211 B CN 101764211B CN 200910019320 A CN200910019320 A CN 200910019320A CN 200910019320 A CN200910019320 A CN 200910019320A CN 101764211 B CN101764211 B CN 101764211B
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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 preparation method of spherical lithium manganese for lithium-ion battery cathode material, which belongs to the technical field of new energy material. Lithium carbonate or acteate and manganese dioxide are mixed with water by a certain ratio, stirred to prepare rheology phase, dried and sintered for 2h at 700DEG C to prepare primary particles of lithium manganese; the primary particles and methyl cellulose MC water solution are mixed to prepare aqueous phase; and then kerosene serves as oil phase, Span80 serves as surfactant, and the two are stirred to prepare microemulsion, and the microemulsion is heated at 870DEG C and sintered to prepare the secondary particles of lithium manganese. By adopting the technical scheme, the method effectively controls the micro-particle size of lithium manganese spherical sizes by controlling the sintering time of the secondary particles of lithium manganese. The preparation method is simple, the raw material is easily available, the prepared products have excellent physical chemical and clectrochemical properties and are excellent lithium-ion battery cathode material.
Description
Technical field
The present invention relates to a kind of preparation method who is used for the spherical lithium manganate of anode material for lithium-ion batteries, belong to the new energy materials technical field.
Background technology
The anode material for lithium-ion batteries that uses at present and study mainly contains: LiCoO
2, lithium nickel oxygen LiNiO
2, lithium manganese oxygen LiMn
2O
4Three kinds, LiCoO wherein
2Operating voltage with good electrochemical and 3.6V, technology maturation is the matured product on the market.LiNiO
2The advantage that price and reserves are arranged, but operating voltage is low, and the preparation difficulty is big.LiMn2O4 LiMn
2O
4Cheap, operating voltage is high, and self discharge is little, and advantages such as safety non-pollution are the first-selected positive electrodes of lithium ion battery.
But along with lithium ion battery constantly develops to the direction of high-energy-density, anodal material volume specific capacity has been proposed requirement, spheroidization is the effective way that improves the positive electrode volume and capacity ratio.Institute of Nuclear and New Energy Technology, Tsing University adopts crystallization control solid phase reaction new technology (being called for short the crystallization control technology) high-density spherical LiCoO
2, LiNi
0.8Co
0.2O
2, LiMn
2O
4, LiNi
1/3Mn
1/3O
2, LiFePO
4Positive electrode; They also adopt sol-gel technique to synthesize spherical LiV in addition
3O
8And LiFePO
4
The approach of preparation sphere material mainly contains three kinds at present, and first kind is to realize through strictness control crystal growth, like the crystallization control technology; Second kind is through creating the environment of two-phase coexistent, realizing spheroidization thereby utilize interface energy to tend to minimum stable rule, like spray drying; Both combine the realization spheroidization with the front exactly for the third.When the emulsion method secondary granulation utilized two-phase coexistent exactly, interface energy trend minimum principle realized balling-up, and its process nature is a physical process.
Summary of the invention
The object of the invention just provides a kind of simple novel physical preparation method that is used for the spherical lithium manganate of anode material for lithium-ion batteries; This method can obtain spherical LiMn2O4, can also further realize the effective control to LiMn2O4 powder microcosmic size.
Its processing step of the present invention is following:
1), with lithium carbonate and manganese dioxide in molar ratio 1:2 mix with deionized water, stir 2h, obtain the rheology phase, fully stir, reactant is mixed; Reactant is placed in the drying box 80
OC6h, moisture is removed in oven dry; With the oven dry after product 700
OCFollowing microwave sintering, the primary particle of LiMn2O4;
2), the primary particle of LiMn2O4 is mixed with methylated cellulose aqueous solution, obtain mixing water, wherein the mass ratio of LiMn2O4 and water is 1:1;
3), be oil phase with kerosene, Span80 is a surfactant, and water and oil phase are under agitation mixed, and obtains w/o type emulsion; Then this emulsion is heated to 80-90
oC; At last 870
oSintering gets aggregate and is the LiMn2O4 second particle under the C 6h.
Described lithium source is lithium carbonate or lithium acetate, and the LiMn2O4 second particle is spherical pattern, average grain diameter 20～50 μ m, even particle distribution.
Described raw material manganese dioxide is electrolytic manganese dioxide or chemical manganese bioxide.
Adopt in lithium carbonate or the acetic acid and obtain rheology mutually with water mixing, stirring by a certain percentage with manganese dioxide, oven dry is 700
OCMicrowave sintering 2h obtains the primary particle of LiMn2O4, and primary particle and methylcellulose MC aqueous solution are got water, is oil phase again with kerosene, and Span80 is a surfactant, stir microemulsion, the heating 870
oThe C sintering gets the second particle of LiMn2O4.
Adopt above scheme,, realize effective control of LiMn2O4 spheric granules microcosmic size through the sintering time of second particle of control LiMn2O4.
Shown in the SEM photo of method gained of the present invention, product is a granule-morphology, about the about 300nm of average grain diameter, and sintering 12h products therefrom.
Embodiment
It is the primary particle that reaction raw materials gets LiMn2O4 that the present invention selects manganese acetate or manganese carbonate and manganese dioxide; With kerosene is oil phase, and Span80 is a surfactant, with the primary particle and the first class cellulose MC aqueous solution of LiMn2O4 be made into into emulsion mutually.Its preparation process was divided into for two steps.
Embodiment 1
, with lithium carbonate and manganese dioxide in molar ratio 1:2 mix with deionized water, stir 2h, obtain the rheology phase, fully stir, reactant is mixed.Reactant is placed in the drying box 80
OC6h, moisture is removed in oven dry.With the oven dry after product 700
OCFollowing microwave sintering, the primary particle of LiMn2O4.
, with the primary particle and methylcellulose (MC) aqueous solution of LiMn2O4, obtain mixing water, wherein the mass ratio of LiMn2O4 and water is 1:1.
⑶, be oil phase with kerosene, Span80 is a surfactant, and water and oil phase are under agitation mixed, and obtains w/o type emulsion.Then this emulsion is heated to 80-90
oC.At last 870
oSintering gets aggregate and is the LiMn2O4 second particle under the C 6h.
The granule-morphology of product LiMn2O4 is spherical, is evenly distributed the about 20-50 μ of average grain diameter size m.
Embodiment 2
, with lithium carbonate and manganese dioxide in molar ratio 1:2 mix with deionized water, stir 2h, obtain the rheology phase, fully stir, reactant is mixed.Reactant is placed in the drying box 80
OC6h, moisture is removed in oven dry.With the oven dry after product 700
OCFollowing microwave sintering, the primary particle of LiMn2O4.
, with the primary particle and methylcellulose (MC) aqueous solution of LiMn2O4, obtain mixing water, wherein the mass ratio of LiMn2O4 and water is 1:1.
⑶, be oil phase with kerosene, Span80 is a surfactant, and water and oil phase are under agitation mixed, and obtains w/o type emulsion.Then this emulsion is heated to 80-90
oC.At last 870
oThe 12h sintering gets aggregate and is the LiMn2O4 second particle under the C.
The particle agglomeration of product LiMn2O4 is apparent in view, even, and the balling-up effect is not so good as sintering 6h, and many cavities are arranged on the aggregate, is that primary particle reaches the gap that stays after the fusion in sintering process.But this shows that the secondary agglomeration body fusion of crystal has taken place and grown up under high temperature sintering.
Claims (3)
1. preparation method who is used for the spherical lithium manganate of anode material for lithium-ion batteries is characterized in that its processing step is following:
1), with lithium carbonate and manganese dioxide in molar ratio 1:2 mix with deionized water, stir 2h, obtain the rheology phase, fully stir, reactant is mixed; Reactant is placed in the drying box 80
oC 6h, moisture is removed in oven dry; With the oven dry after product 700
oMicrowave sintering under the C, the primary particle of LiMn2O4;
2), the primary particle of LiMn2O4 is mixed with methylated cellulose aqueous solution, obtain mixing water, wherein the mass ratio of LiMn2O4 and water is 1:1;
3), be oil phase with kerosene, Span80 is a surfactant, and water and oil phase are under agitation mixed, and obtains w/o type emulsion; Then this emulsion is heated to 80-90
oC; At last 870
oSintering gets aggregate and is the LiMn2O4 second particle under the C 6h.
2. a kind of preparation method who is used for the spherical lithium manganate of anode material for lithium-ion batteries according to claim 1 is characterized in that: the LiMn2O4 second particle of step 3) is spherical pattern, average grain diameter 20～50 μ m, even particle distribution.
3. a kind of preparation method who is used for the spherical lithium manganate of anode material for lithium-ion batteries according to claim 2 is characterized in that described raw material manganese dioxide is electrolytic manganese dioxide or chemical manganese bioxide.
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| CN101764211B true CN101764211B (en) | 2012-10-03 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101913655B (en) * | 2010-09-10 | 2012-07-04 | 河南联合新能源有限公司 | Method for preparing lithium manganate cathode material by microwave sintering |
| CN102820462A (en) * | 2012-08-24 | 2012-12-12 | 安徽亚兰德新能源材料股份有限公司 | Preparation process of anode material lithium manganate of spherical structure for lithium ion battery |
| CN104183839A (en) * | 2013-05-22 | 2014-12-03 | 无锡晶石新型能源有限公司 | Lithium manganate fine particle processing method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1453889A (en) * | 2002-04-26 | 2003-11-05 | 江苏海四达集团有限公司 | Drying and melting process of preparing LiMn2O4 latex as positive electrode material for lithium ion battery |
| CN1743276A (en) * | 2004-08-31 | 2006-03-08 | 比亚迪股份有限公司 | Lithium cell anode material lithium manganate preparing method |
-
2009
- 2009-10-14 CN CN200910019320A patent/CN101764211B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1453889A (en) * | 2002-04-26 | 2003-11-05 | 江苏海四达集团有限公司 | Drying and melting process of preparing LiMn2O4 latex as positive electrode material for lithium ion battery |
| CN1743276A (en) * | 2004-08-31 | 2006-03-08 | 比亚迪股份有限公司 | Lithium cell anode material lithium manganate preparing method |
Non-Patent Citations (1)
| Title |
|---|
| Kwang-Taek Hwang et al..Powder synthesis and electrochemical properties of LiMn2O4 prepared by an emulsion-drying method.《Journal of Power Sources》.1998,第74卷169-174. * |
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Owner name: QINGDAO QIANYUN HIGH-TECH NEW MATERIAL CO., LTD. Free format text: FORMER OWNER: SUN QI Effective date: 20120604 |
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Effective date of registration: 20120604 Address after: Chengyang Qingda Industrial Park, 266111 Shandong middle road Fengyuan City in Qingdao Province Applicant after: QingDao Qianyun High-tech New Material Co., Ltd. Address before: Chengyang Qingda Industrial Park, 266111 Shandong middle road Fengyuan City in Qingdao province Qingdao qianyun hi tech new material Co. Ltd. Applicant before: Sun Qi |
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Denomination of invention: Preparation method of spherical lithium manganese for lithium-ion battery cathode material Effective date of registration: 20200629 Granted publication date: 20121003 Pledgee: China Construction Bank Corporation Qingdao Zhongshan Road sub branch Pledgor: QINGDAO QIANYUN HIGH-TECH NEW MATERIAL Co.,Ltd. Registration number: Y2020370010025 |