CN102544471A - Method for preparing lithium manganate anode material - Google Patents
Method for preparing lithium manganate anode material Download PDFInfo
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- CN102544471A CN102544471A CN2011104456999A CN201110445699A CN102544471A CN 102544471 A CN102544471 A CN 102544471A CN 2011104456999 A CN2011104456999 A CN 2011104456999A CN 201110445699 A CN201110445699 A CN 201110445699A CN 102544471 A CN102544471 A CN 102544471A
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- lithium
- manganese
- cathode material
- lithium manganate
- manganate
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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 method for preparing lithium battery anode material, in particular to a method for preparing lithium manganate anode material. The method is characterized by comprising the following steps of: (1) adding soluble lithium salt, manganic compound and doping agent into deionized water for stirring according to a mol ratio of (0.5-0.65):(1-1.2):(0.01-0.02); (2) spraying pyrolyzing the obtained mixed liquid according to a spraying dryer; (3) placing the mixed liquid into a microwave sintering furnace, heating for 6-8 hours under 2-4kW, and keeping for 5-8 hours under 800-1000W so as to obtain lithium manganate; and (4) washing by pure water and filtering for at least three times, drying under 130-150 DEG C, and screening by a 200-mesh sieve so as to obtain the lithium manganate anode material. According to the method, the material is directly heated through microwave sintering, so that the material is evenly heated, and the particles are uniform; the crystallinity is better; the product quality is improved; and the method is good for preparing lithium manganate with stable performance.
Description
Technical field
The present invention relates to the preparation of anode material of lithium battery, especially a kind of preparation method of manganate cathode material for lithium.
Background technology
In lithium ion battery, positive electrode is its most important component, also is the key of decision lithium ion battery performance.Spinel-type LiMn
2O
4Be in recent years by one of lithium ion utmost point material of extensive concern, use positive electrode LiCoO with present commerce
2Compare have aboundresources, advantage such as cheap, nontoxic pollution-free; The agent structure of spinel lithium manganate is done cube tightly packed composition of rule by oxonium ion; Lithium ion and manganese ion occupy respectively in tetrahedron and octahedral interstices, and its simplest formula is LiMn
2O
4, the sky with Fd3m (No.227) is asked the crowd, lithium ion is distributed in the 3 D pore canal around the manganese oxygen octahedra, thereby guarantees its migration in the duct, makes charge and discharge process have excellent cycle performance.
Spinel-type LiMn
2O
4Embedding with respect to lithium metal. deviate from current potential about 4V, with LiCoO
2And LiNiO
2Approaching.The ABUNDANT NATUREAL RESOURSES of manganese can keep low-cost in a large amount of uses of lithium ion battery.And the history that manganese compound uses in battery industry is very long, and experienced to the processing of manganese compound and recovery can not caused very big pollution to environment.Research shows that synthetic method has significant effects to product structure and performance, therefore, develops new method and prepares spinel-type LiMn
2O
4Material becomes one of important channel of improving its performance.
Be commonly used to prepare LiMn at present
2O
4Method be mainly conventional solid-state method, the method simple and fast, but batch mixing is uneven, raw material is heated inhomogeneous, product cut size is inhomogeneous, thing phase purity is limited to, and power consumption is huge, the cost greater energy consumption is big, properties of product are relatively poor.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of manganate cathode material for lithium can access the uniform LiMn2O4 of degree of crystallinity, less, the uniformity of while particle diameter, and it is inhomogeneous also to have avoided the synthetic middle material of electric furnace sintering to be heated, and has obviously reduced sintering time simultaneously.
A kind of preparation method of manganate cathode material for lithium, its special feature is, comprises the steps:
(1) according to the solubility lithium salts: the compound of manganese: dopant=(0.5～0.65): (1～1.2): the mol ratio of (0.01～0.02) joins is enough to make the consoluet deionized water for stirring of mentioned component that it is mixed;
(2) the gained mixed liquor is passed through the spray dryer spray pyrolysis, obtain the mixed uniformly manganate precursor for lithium powder of material;
(3) the gained precursor powder is placed in the microwave agglomerating furnace,, keep 5～8h with 800～1000W again, promptly get LiMn2O4 with 2～4kW heating, 6～8h;
(4) gained LiMn2O4 sample is washed, filters at least three times through pure water, through 130～150 ℃ of oven dry, promptly get manganate cathode material for lithium then after 200 mesh sieves.
Presoma is that method sedimentation through spray pyrolysis obtains in the step (2).
Solubility lithium salts in the step (1) is at least a in lithium nitrate, lithium sulfate, lithium acetate and the lithium halide; The compound of manganese is at least a in manganese dioxide, manganese nitrate and the manganese acetate, and dopant is to be selected from MgCO
3, Cr
2O
3, Al
2O
3, Co
2O
3, V
2O
5At least a with in the rare earth oxide.
The present invention prepares uniform manganate precursor for lithium through the method for spray pyrolysis sedimentation, and the method for this process using mixed reactant in liquid phase realizes the mixing of storeroom molecular level, and in spray-dired process; Making moisture by oven dry rapidly, is the nuclei of condensation with manganese, and other elemental substances settle down with powder morphology attached to around the nuclei of condensation; Reach mixed uniformly purpose, through microwave sintering, material is directly heated again, make material be heated evenly; The product particle is uniformity more, and degree of crystallinity is better, promotes product quality, helps the stable LiMn2O4 of processability; And can save the energy, shorten the production cycle, enhance productivity.
Description of drawings
Fig. 1 is the XRD figure of synthetic sample among the embodiment 1, can find out that the degree of crystallinity of sample is high, and crystalline phase is purer;
Fig. 2 is the SEM shape appearance figure of synthetic sample among the embodiment 1, can find out regular particles, and particle diameter is even.
Embodiment
To achieve these goals, the present invention realizes through following technical proposals, mainly passes through the method for spray pyrolysis sedimentation, the manganate precursor for lithium that is uniformly mixed, and then carry out microwave sintering, make the uniform manganate cathode material for lithium of particle diameter.
Embodiment 1
1) with lithium carbonate, manganese dioxide, magnesium carbonate according to Li: Mn: Mg=0.6: 1.1: 0.015 mol ratio joins in the deionized water, stirs, and evenly mixes.
2) the gained mixed liquor is obtained the mixed uniformly manganate precursor for lithium powder of material after through the spray dryer spray pyrolysis.
3) the gained precursor powder places in the microwave agglomerating furnace, with 3kW heating 7h, keeps 6h with 900W again, promptly gets the uniform mutually LiMn2O4 of better crystallinity degree, thing.
4) above-mentioned gained LiMn2O4 sample is washed, filters three times through pure water,, and then cross 200 mesh sieves, obtain colory manganate cathode material for lithium through 140 ℃ of oven dry.
The present invention is as shown in Figure 1 through the XRD figure of the sample of the foregoing description 1, and thing is very pure mutually, and degree of crystallinity is also fine, and its pattern is as shown in Figure 2.
1) with lithium carbonate, manganese dioxide, magnesium carbonate according to Li: Mn: Mg=0.5: 1: 0.01 mol ratio joins in the deionized water, stirs, and evenly mixes.
2) the gained mixed liquor is obtained the mixed uniformly manganate precursor for lithium powder of material after through the spray dryer spray pyrolysis.
3) the gained precursor powder places in the microwave agglomerating furnace, with 2kW heating 8h, keeps 8h with 800W again, promptly gets the uniform mutually LiMn2O4 of better crystallinity degree, thing.
4) above-mentioned gained LiMn2O4 sample is washed, filters three times through pure water,, and then cross 200 mesh sieves, obtain colory manganate cathode material for lithium through 130 ℃ of oven dry.
1) with lithium carbonate, manganese dioxide, magnesium carbonate according to Li: Mn: Mg=0.65: 1.2: 0.02 mol ratio joins in the deionized water, stirs, and evenly mixes.
2) the gained mixed liquor is obtained the mixed uniformly manganate precursor for lithium powder of material after through the spray dryer spray pyrolysis.
3) the gained precursor powder places in the microwave agglomerating furnace, with 4kW heating 6h, keeps 5h with 1000W again, promptly gets the uniform mutually LiMn2O4 of better crystallinity degree, thing.
4) above-mentioned gained LiMn2O4 sample is washed, filters three times through pure water,, and then cross 200 mesh sieves, obtain colory manganate cathode material for lithium through 150 ℃ of oven dry.
Embodiment 4
1) with lithium carbonate, manganese dioxide and manganese nitrate mixture (mol ratio is 1: 1), magnesium carbonate according to Li: Mn: Mg=0.65: 1.2: 0.02 mol ratio joins in the deionized water, stirs, and evenly mixes.
2) the gained mixed liquor is obtained the mixed uniformly manganate precursor for lithium powder of material after through the spray dryer spray pyrolysis.
3) the gained precursor powder places in the microwave agglomerating furnace, with 3kW heating 6h, keeps 5h with 1000W again, promptly gets the uniform mutually LiMn2O4 of better crystallinity degree, thing.
4) above-mentioned gained LiMn2O4 sample is washed, filters three times through pure water,, and then cross 200 mesh sieves, obtain colory manganate cathode material for lithium through 150 ℃ of oven dry.
Claims (3)
1. the preparation method of a manganate cathode material for lithium is characterized in that, comprises the steps:
(1) according to the solubility lithium salts: the compound of manganese: dopant=(0.5～0.65): (1～1.2): the mol ratio of (0.01～0.02) joins is enough to make the consoluet deionized water for stirring of mentioned component that it is mixed;
(2) the gained mixed liquor is passed through the spray dryer spray pyrolysis, obtain the mixed uniformly manganate precursor for lithium powder of material;
(3) the gained precursor powder is placed in the microwave agglomerating furnace,, keep 5～8h with 800～1000W again, promptly get LiMn2O4 with 2～4kW heating, 6～8h;
(4) gained LiMn2O4 sample is washed, filters at least three times through pure water, through 130～150 ℃ of oven dry, promptly get manganate cathode material for lithium then after 200 mesh sieves.
2. the preparation method of a kind of manganate cathode material for lithium as claimed in claim 1 is characterized in that: presoma is that method sedimentation through spray pyrolysis obtains in the step (2).
3. according to claim 1 or claim 2 a kind of preparation method of manganate cathode material for lithium is characterized in that: the solubility lithium salts in the step (1) is at least a in lithium nitrate, lithium sulfate, lithium acetate and the lithium halide; The compound of manganese is at least a in manganese dioxide, manganese nitrate and the manganese acetate, and dopant is to be selected from MgCO
3, Cr
2O
3, Al
2O
3, Co
2O
3, V
2O
5At least a with in the rare earth oxide.
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| CN2011104456999A CN102544471A (en) | 2011-12-27 | 2011-12-27 | Method for preparing lithium manganate anode material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103066270A (en) * | 2012-12-28 | 2013-04-24 | 湘潭大学 | Preparation method of nano-spinel type LiMn2O4 |
| CN105932269A (en) * | 2016-05-24 | 2016-09-07 | 浙江美达瑞新材料科技有限公司 | Method for preparing positive electrode material for lithium ion cell by spraying, combusting and pyrolyzing |
| CN111613446A (en) * | 2020-06-05 | 2020-09-01 | 南通海星电子股份有限公司 | Formation treatment method of high-water-resistance low-pressure aluminum foil |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5770018A (en) * | 1996-04-10 | 1998-06-23 | Valence Technology, Inc. | Method for preparing lithium manganese oxide compounds |
| CN1805182A (en) * | 2005-01-14 | 2006-07-19 | 湖南瑞翔新材料有限公司 | New preparation method of positive and negative electrode materials of lithium ion secondary cell by spraying thermal decomposition |
| CN101459239A (en) * | 2007-12-14 | 2009-06-17 | 中国电子科技集团公司第十八研究所 | Preparation for lithium battery anode active material |
-
2011
- 2011-12-27 CN CN2011104456999A patent/CN102544471A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5770018A (en) * | 1996-04-10 | 1998-06-23 | Valence Technology, Inc. | Method for preparing lithium manganese oxide compounds |
| CN1805182A (en) * | 2005-01-14 | 2006-07-19 | 湖南瑞翔新材料有限公司 | New preparation method of positive and negative electrode materials of lithium ion secondary cell by spraying thermal decomposition |
| CN101459239A (en) * | 2007-12-14 | 2009-06-17 | 中国电子科技集团公司第十八研究所 | Preparation for lithium battery anode active material |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103066270A (en) * | 2012-12-28 | 2013-04-24 | 湘潭大学 | Preparation method of nano-spinel type LiMn2O4 |
| CN103066270B (en) * | 2012-12-28 | 2015-07-22 | 湘潭大学 | Preparation method of nano-spinel type LiMn2O4 |
| CN105932269A (en) * | 2016-05-24 | 2016-09-07 | 浙江美达瑞新材料科技有限公司 | Method for preparing positive electrode material for lithium ion cell by spraying, combusting and pyrolyzing |
| CN105932269B (en) * | 2016-05-24 | 2019-04-30 | 浙江美达瑞新材料科技有限公司 | The method that spray burning pyrolysis prepares anode material for lithium-ion batteries |
| CN111613446A (en) * | 2020-06-05 | 2020-09-01 | 南通海星电子股份有限公司 | Formation treatment method of high-water-resistance low-pressure aluminum foil |
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Application publication date: 20120704 |