CN104064754B - A kind of preparation method of lithium manganese oxide - Google Patents
A kind of preparation method of lithium manganese oxide Download PDFInfo
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- CN104064754B CN104064754B CN201410315723.0A CN201410315723A CN104064754B CN 104064754 B CN104064754 B CN 104064754B CN 201410315723 A CN201410315723 A CN 201410315723A CN 104064754 B CN104064754 B CN 104064754B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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 discloses a kind of preparation method of lithium manganese oxide. Preparation method comprises following step: (1), by water heating, adds lithium metasilicate, uses hydrochloric acid conditioning solution PH, adds the hydroxide reaction of manganese, obtains mixed slurry, leaves standstill, and removes upper strata moisture; (2) mixed slurry is calcined to 2-3h under the condition of oxygen enrichment, obtain compound crude product; (3) after compound crude product is naturally cooling, be placed in ball mill ball milling, obtain slurry, leave standstill, remove upper strata moisture; (4) slurry is calcined to 1-2h under the condition of oxygen enrichment, be sharply cooled to 300-400 DEG C, keep 30-60min, naturally cooling, finally the calcined material dry ball milling obtaining is obtained to lithium manganese oxide; Preparation method of the present invention is simple, and preparation process is pollution-free, energy consumption is low, good operation conditions; Raw material sources are extensive, and preparation cost is low; High and the good uniformity of the lithium manganese oxide purity for preparing, being applied to battery has good cycle characteristics.
Description
Technical field
The present invention relates to a kind of preparation method of lithium manganese oxide, belong to compound preparing technical field.
Background technology
Lithium ion battery is a kind of advanced person's of 21st century green high-capacity environment-protecting type secondary cell, but now widely used lithium cobaltate cathode materialBecause cost is high and the outstanding problem such as poor safety performance can not meet IT industry and the requirement of electric automobile industry to battery performance of high speed development. Lithium manganeseOxide is because of aboundresources, low price, and safety and environmental protection performance is good, is acknowledged as one of positive electrode of the most potential substituting cobalt acid lithium.
Tradition solid reaction process directly adopts lithium salts and manganese salt mixed calcining to prepare lithium manganese compound, but this method products therefrom particle is large and inhomogeneous, changesLearn metering and control than difficult, reaction temperature is high, the time is long, cost is high, and easily causes the loss of lithium.
Summary of the invention
The present invention seeks to: the preparation method that a kind of lithium manganese oxide is provided.
Technical scheme of the present invention is:
A preparation method for lithium manganese oxide, comprises following step:
(1) heat water to 60-80 DEG C, add lithium metasilicate, obtain colourless transparent liquid, with hydrochloric acid conditioning solution PH be 8-9, add manganeseHydroxide, under the condition of rapid stirring, reaction 2-3h, obtains mixed slurry, and mixed slurry is left standstill to 6-8h, removes upper strata moisture;
(2) be 300-400 DEG C by the mixed slurry of removing after the moisture of upper strata in temperature, under the condition of oxygen enrichment, calcine 2-3h, obtain compound crude product,Described compound crude product D50 is 10-15 μ m, and its specific area is 0.05-0.15m2/g；
(3) after compound crude product is naturally cooling, be placed in ball mill ball milling, the weight ratio of ball, water and slurry is 6-8: 3-4: 1, and ball milling 2-3hObtain slurry, leave standstill 6-8h, remove upper strata moisture;
(4) be 500-600 DEG C by the slurry of removing after the moisture of upper strata in temperature, under the condition of oxygen enrichment, calcine 1-2h, be sharply cooled to 300-400DEG C, keep 30-60min, naturally cooling, finally the calcined material dry ball milling obtaining is obtained to lithium manganese oxide;
Wherein, the weight ratio of the hydroxide of lithium metasilicate and manganese is 1: 2.
The chemical formula of the hydroxide of described manganese is Mn (OH)3。
The preparation method of described a kind of lithium manganese oxide, the percentage by weight of lithium metasilicate aqueous solution mesosilicic acid lithium is 10-14%.
The preparation method of described a kind of lithium manganese oxide, in step (1), mixing speed is 200-400 rev/min.
The layered lithium manganese oxide obtaining according to the preparation method of described a kind of lithium manganese oxide, the D50 of described lithium manganese oxide is 2-5 μ m,Its specific area is 0.3-0.5m2/ g, tap density is 1.2-2.0g/cm3, interlamellar spacing is 20-25nm, its chemical formula is LiMnO4。
Advantage of the present invention is:
1. preparation method is simple, and the hydroxide by lithium metasilicate and manganese first mixes under weak basic condition, then through the side of calcining-ball milling-calciningMethod, does not add any dispersant, additive, can control the lithium manganese oxide that obtains having certain particle size and interlamellar spacing, has both solved simple high temperatureSolid phase method products obtained therefrom size distribution, interlamellar spacing uniformity are poor, have solved again the not high problem of electrochemical process products obtained therefrom activity, and preparation process is without dirtDye, reduced calcining heat, energy consumption is low, good operation conditions.
2. prepare required lithium metasilicate and the equal wide material sources of hydroxide of manganese, in the process of preparing mixed slurry, coordinate the adjusting for pH value,Can control particle diameter, specific area and the tap density of product.
3. the high and good uniformity of the lithium manganese oxide purity for preparing; The D50 of the lithium manganese oxide preparing is 2-5 μ m, its specific areaFor 0.3-0.5m2/ g, tap density is 1.2-2.0g/cm3, interlamellar spacing is 20-25nm, its chemical formula is LiMnO4. Specific energy is after testing175-185Wh/Kg, normal temperature circulation time, 10 attenuation rates are 0.005-0.015%.
Detailed description of the invention
Embodiment 1
A preparation method for lithium manganese oxide, comprises following step:
(1) heat water to 80 DEG C, add lithium metasilicate, obtain colourless transparent liquid, with hydrochloric acid conditioning solution PH be 8-9, add the hydrogen-oxygen of manganeseCompound, under the condition of rapid stirring, reaction 2h, obtains mixed slurry, and mixed slurry is left standstill to 8h, removes upper strata moisture;
(2) be 400 DEG C by the mixed slurry of removing after the moisture of upper strata in temperature, under the condition of oxygen enrichment, calcine 2h, obtain compound crude product, described inCompound crude product D50 is 10 μ m, and its specific area is 0.05m2/g；；
(3) after compound crude product is naturally cooling, be placed in ball mill ball milling, the weight ratio of ball, water and slurry is 6: 3: 1, and ball milling 2h obtainsSlurry, leaves standstill 8h, removes upper strata moisture;
(4) be 600 DEG C by the slurry of removing after the moisture of upper strata in temperature, under the condition of oxygen enrichment, calcine 1h, be sharply cooled to 400 DEG C, keep 30min,Naturally cooling, finally the calcined material dry ball milling obtaining is obtained to lithium manganese oxide;
Wherein, the weight ratio of the hydroxide of lithium metasilicate and manganese is 1: 2.
The chemical formula of the hydroxide of described manganese is Mn (OH)3。
The preparation method of described a kind of lithium manganese oxide, the percentage by weight of lithium metasilicate aqueous solution mesosilicic acid lithium is 10%.
The preparation method of described a kind of lithium manganese oxide, in step (1), mixing speed is 200 revs/min.
The D50 of the lithium manganese oxide preparing is 5 μ m, and its specific area is 0.5m2/ g, tap density is 1.2g/cm3, interlamellar spacing is 25nm,Its chemical formula is LiMnO4. Specific energy is 175Wh/Kg after testing, normal temperature circulation time, and 10 times attenuation rate is 0.015%.
Comparative example 1
Comparative example 1 is identical with embodiment 1 condition, and what while being ball milling, take is dry ball milling, and the D50 of the lithium manganese oxide finally obtaining is 15μ m, its specific area is 0.1m2/ g, tap density is 1.0g/cm3, interlamellar spacing is 18nm, its chemical formula is LiMnO4。
Embodiment 2
A preparation method for lithium manganese oxide, comprises following step:
(1) heat water to 60 DEG C, add lithium metasilicate, obtain colourless transparent liquid, with hydrochloric acid conditioning solution PH be 8-9, add the hydrogen-oxygen of manganeseCompound, under the condition of rapid stirring, reaction 3h, obtains mixed slurry, and mixed slurry is left standstill to 6h, removes upper strata moisture;
(2) be 300 DEG C by the mixed slurry of removing after the moisture of upper strata in temperature, under the condition of oxygen enrichment, calcine 3h, obtain compound crude product, described inCompound crude product D50 is 15 μ m, and its specific area is 0.15m2/g；；
(3) after compound crude product is naturally cooling, be placed in ball mill ball milling, the weight ratio of ball, water and slurry is 8: 4: 1, and ball milling 3h obtainsSlurry, leaves standstill 6h, removes upper strata moisture;
(4) be 500 DEG C by the slurry of removing after the moisture of upper strata in temperature, under the condition of oxygen enrichment, calcine 2h, be sharply cooled to 300 DEG C, keep 60min,Naturally cooling, finally the calcined material dry ball milling obtaining is obtained to lithium manganese oxide;
Wherein, the weight ratio of the hydroxide of lithium metasilicate and manganese is 1: 2.
The chemical formula of the hydroxide of described manganese is Mn (OH)3。
The preparation method of described a kind of lithium manganese oxide, the percentage by weight of lithium metasilicate aqueous solution mesosilicic acid lithium is 14%.
The preparation method of described a kind of lithium manganese oxide, in step (1), mixing speed is 400 revs/min.
The D50 of the lithium manganese oxide preparing is 2 μ m, and its specific area is 0.3m2/ g, tap density is 2.0g/cm3, interlamellar spacing is 20nm,Its chemical formula is LiMnO4. Specific energy is 185Wh/Kg after testing, normal temperature circulation time, and 10 times attenuation rate is 0.005%.
Comparative example 2
Comparative example 2 is identical with embodiment 2 conditions, and just calcining is under the condition of air, and the D50 of the lithium manganese oxide finally obtaining is 2 μ m,Its specific area is 0.3m2/ g, tap density is 2.0g/cm3, interlamellar spacing is 10nm, its chemical formula is LiMnO2。
Embodiment 3
A preparation method for lithium manganese oxide, comprises following step:
(1) heat water to 65 DEG C, add lithium metasilicate, obtain colourless transparent liquid, with hydrochloric acid conditioning solution PH be 8-9, add the hydrogen-oxygen of manganeseCompound, under the condition of rapid stirring, reaction 2h, obtains mixed slurry, and mixed slurry is left standstill to 6h, removes upper strata moisture;
(2) be 400 DEG C by the mixed slurry of removing after the moisture of upper strata in temperature, under the condition of oxygen enrichment, calcine 2h, obtain compound crude product, described inCompound crude product D50 is 12 μ m, and its specific area is 0.12m2/g；
(3) after compound crude product is naturally cooling, be placed in ball mill ball milling, the weight ratio of ball, water and slurry is 8: 3: 1, and ball milling 3h obtainsSlurry, leaves standstill 6h, removes upper strata moisture;
(4) be 600 DEG C by the slurry of removing after the moisture of upper strata in temperature, under the condition of oxygen enrichment, calcine 1-2h, be sharply cooled to 400 DEG C, keep60min, naturally cooling, finally the calcined material dry ball milling obtaining is obtained to lithium manganese oxide;
Wherein, the weight ratio of the hydroxide of lithium metasilicate and manganese is 1: 2.
The chemical formula of the hydroxide of described manganese is Mn (OH)3。
The preparation method of described a kind of lithium manganese oxide, the percentage by weight of lithium metasilicate aqueous solution mesosilicic acid lithium is 12%.
The preparation method of described a kind of lithium manganese oxide, in step (1), mixing speed is 300 revs/min.
The D50 of the lithium manganese oxide preparing is 4 μ m, and its specific area is 0.4m2/ g, tap density is 1.8g/cm3, interlamellar spacing is 22nm,Its chemical formula is LiMnO4. Specific energy is 180Wh/Kg after testing, normal temperature circulation time, and 10 attenuation rates are 0.005-0.01%.
Comparative example 3
Comparative example 3 is identical with embodiment 3 conditions, has just saved the step that regulates PH with hydrochloric acid, and the D50 of the lithium manganese oxide finally obtaining is10 μ m, its specific area is 0.05m2/ g, tap density is 2.5g/cm3, interlamellar spacing is 20nm, its chemical formula is LiMnO4。
More than show and described general principle of the present invention and principal character and advantage of the present invention. The technical staff of the industry should understand, thisBrightly be not restricted to the described embodiments, that in above-described embodiment and description, describes just illustrates principle of the present invention, do not depart from the present invention's spirit andUnder the prerequisite of scope, the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention. The present inventionClaimed scope is defined by appending claims and equivalent thereof.
Claims (4)
1. a preparation method for lithium manganese oxide, is characterized in that, comprises following step:
(1) heat water to 60-80 DEG C, add lithium metasilicate, obtain colourless transparent liquid, use hydrochloric acid conditioning solution pHFor 8-9, add the hydroxide of manganese, under the condition of rapid stirring, reaction 2-3h, obtains mixed slurry,Mixed slurry is left standstill to 6-8h, remove upper strata moisture;
(2) under being 300-400 DEG C, the condition of oxygen enrichment, temperature calcines 2-3h by removing mixed slurry after the moisture of upper strata,Obtain compound crude product, described compound crude product D50 is 10-15 μ m, and its specific area is0.05-0.15m2/g；
(3) after compound crude product is naturally cooling, be placed in ball mill ball milling, the weight ratio of ball, water and slurry is6-8: 3-4: 1, ball milling 2-3h obtains slurry, leaves standstill 6-8h, removes upper strata moisture;
(4) under being 500-600 DEG C, the condition of oxygen enrichment, temperature calcines 1-2h by removing slurry after the moisture of upper strata, sharplyBe cooled to 300-400 DEG C, keep 30-60min, naturally cooling, finally the calcined material dry ball milling obtaining is obtainedTo lithium manganese oxide LiMnO4；
Wherein, the weight ratio of the hydroxide of lithium metasilicate and manganese is 1: 2; The chemistry of the hydroxide of described manganeseFormula is Mn (OH)3。
2. the preparation method of a kind of lithium manganese oxide according to claim 1, is characterized in that, lithium metasilicate waterThe percentage by weight of solution mesosilicic acid lithium is 10-14%.
3. the preparation method of a kind of lithium manganese oxide according to claim 1, is characterized in that, step is stirred in (1)The speed of mixing is 200-400 rev/min.
4. the layered lithium manganese oxide that the preparation method of a kind of lithium manganese oxide according to claim 1 obtains, instituteThe D50 of the lithium manganese oxide of stating is 2-5 μ m, and its specific area is 0.3-0.5m2/ g, tap density is1.2-2.0g/cm3, interlamellar spacing is 20-25nm.
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| CN1089193C (en) * | 1998-10-09 | 2002-08-14 | 清华大学 | Method for preparing lithium ion battery active material superfines with spray drying method |
| KR100603303B1 (en) * | 2003-10-29 | 2006-07-20 | 삼성에스디아이 주식회사 | Lithium battery having effective performance |
| CN1805179A (en) * | 2005-01-13 | 2006-07-19 | 新疆大学 | Preparation method of positive electrode material of lithium ion cell in spinel structure LiCoxMn2-XO4 (0<=X<=0.2) |
| CN101161592A (en) * | 2006-10-12 | 2008-04-16 | 比亚迪股份有限公司 | A method for preparing sphericity manganic acid lithium cell anode active material |
| CN101459237B (en) * | 2007-12-10 | 2012-08-08 | 深圳市比克电池有限公司 | Battery cathode slurry, preparation and battery produced by the cathode slurry |
| EP4068914A3 (en) * | 2009-05-19 | 2022-10-12 | OneD Material, Inc. | Nanostructured materials for battery applications |
| US20110039148A1 (en) * | 2009-08-14 | 2011-02-17 | Yichun Wang | Alkaline primary cells |
| CN102709586B (en) * | 2012-01-12 | 2016-11-09 | 宁德新能源科技有限公司 | A kind of lithium titanate battery |
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