CN102842708A - Manganous-manganic oxide preparation method for battery positive pole material lithium manganate and product thereof - Google Patents
Manganous-manganic oxide preparation method for battery positive pole material lithium manganate and product thereof Download PDFInfo
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- CN102842708A CN102842708A CN2012102877697A CN201210287769A CN102842708A CN 102842708 A CN102842708 A CN 102842708A CN 2012102877697 A CN2012102877697 A CN 2012102877697A CN 201210287769 A CN201210287769 A CN 201210287769A CN 102842708 A CN102842708 A CN 102842708A
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Abstract
The invention discloses a manganous-manganic oxide preparation method for battery positive pole material lithium manganate and a product thereof. After high pure manganese metal powder is crushed in a dry method to a certain particle size distribution, and air is added into a reactor for oxidation after water and ammonium salts are added. In an early stage of reaction, air flow is 20-100 cubic meters per hour; after five hours of the reaction, the air flow is regulated to 40-300 cubic meters per hour; after twelve hours of the reaction, the air flow is regulated to 20-100 cubic meters per hour; and when the reaction is finished, a stirring rate is controlled to be 250-450 revolutions per minute. Time needed for the reaction is 18-28 hours, and a potential of hydrogen (pH) value at a finishing point of the reaction is controlled to be 6.4 +/-0.2. After the reaction is finished completely, a manganous-manganic oxide product can be prepared after being washed and dried. The manganous-manganic oxide product prepared by means of the method is 15-30 micrometers in a particle diameter, 1.0-4.0 square meters per gram in specific surface area, and 2.0-3.0 grams per cubic centimeter in tap density. With the manganous-manganic oxide preparation method, the lithium manganate positive pole material has the advantages of being good in capacity performance, high in compaction density, goof in cycle performance and the like.
Description
Technical field
The present invention relates to a kind of preparation method of the used raw material mangano-manganic oxide of battery positive-material lithium manganate and products thereof.
Background technology
LiMn2O4 (LiMn
2O
4) be one of more promising lithium ion anode material, traditional positive electrodes such as treatment acid lithium, advantages such as LiMn2O4 has aboundresources, cost is low, pollution-free, fail safe is good, good rate capability are desirable power battery anode materials.
LiMn2O4 (LiMn
2O
4) and mangano-manganic oxide (Mn
3O
4) all be spinel structure.With mangano-manganic oxide (Mn
3O
4) replacement electrolytic manganese dioxide (MnO
2) the preparation LiMn2O4, there is not violent structural change, LiMn2O4 (LiMn
2O
4) formation relatively easy, therefore, with mangano-manganic oxide (Mn
3O
4) synthetic LiMn2O4 (LiMn
2O
4) come into one's own gradually.
As preparation LiMn2O4 (LiMn
2O
4) main raw material(s) of positive electrode; The meta particle diameter of mangano-manganic oxide, specific area, tap density, impurity content etc. directly influence the performance of lithium manganate material; The main method of preparation manganor manganic oxide used for soft magnetic ferrite is to adopt the suspension catalytic oxidation at present; The product meta particle diameter of this explained hereafter is on the low side (≤10 μ m), higher (>=4 m of specific area
2/ g), low (≤1.6 g/cm of tap density
3), granule-morphology is irregular, and metals content impurity is high, finally influences volumetric properties, cycle performance and the processability of lithium manganate battery.
Summary of the invention
Problem to be solved by this invention provides battery positive-material lithium manganate with a kind of preparation method of mangano-manganic oxide and products thereof.Because used electrolytic manganese adopts dry method powder process in the method for the present invention, therefore be convenient in the commercial process control, and, make final products granule-morphology homogeneous and controllable through control to particle size distribution to metal impurities.The special-purpose mangano-manganic oxide product of the LiMn2O4 that the inventive method is produced meta particle diameter is 15 μ m ~ 30 μ m, and specific area is 1.0m
2/ g ~ 4.0m
2/ g, tap density is 2.0 g/cm
3~ 3.0g/cm
3
Battery positive-material lithium manganate of the present invention is used METHODS OF MAKING MANGANIC MANGANOUS OXIDE, and its concrete steps are:
With the high pure metal manganese powder with dry milling to certain grain size distribution, in reactor, add blowing air oxidation behind water and the ammonium salt, the initial reaction stage air mass flow is 20 ~ 100 m
3/ h, reaction air mass flow after the 5th hour is adjusted into 40 ~ 300m
3/ h, reaction air mass flow after the 12nd hour is adjusted to 20 ~ 100m
3/ h finishes until reaction, and mixing speed is controlled at 250r/min ~ 450r/min, and the course of reaction required time is 18 ~ 28h, and the reaction end pH value is controlled at 6.4 ± 0.2, after reacting completely, after washing, drying, makes the mangano-manganic oxide product.
The special-purpose mangano-manganic oxide of the LiMn2O4 that utilizes the inventive method to obtain, its meta particle diameter is 15 μ m ~ 30 μ m, specific area is 1.0m
2/ g ~ 4.0m
2/ g, tap density is 2.0 g/cm
3~ 3.0g/cm
3
The present invention can produce the special-purpose mangano-manganic oxide of LiMn2O4 of different impurities content according to customer requirement, and the manganate cathode material for lithium of producing with this mangano-manganic oxide has good, the characteristics such as compacted density is high, good cycle of volumetric properties.
Description of drawings
Fig. 1 is the particle size distribution figure of the embodiment of the invention 1 prepared mangano-manganic oxide product;
Fig. 2 is the sem photograph of the embodiment of the invention 1 prepared mangano-manganic oxide product;
Fig. 3 is the particle size distribution figure of the embodiment of the invention 2 prepared mangano-manganic oxide products;
Fig. 4 is the sem photograph of the embodiment of the invention 2 prepared mangano-manganic oxide products;
Fig. 5 is the particle size distribution figure of the embodiment of the invention 3 prepared mangano-manganic oxide products;
Fig. 6 is the sem photograph of the embodiment of the invention 3 prepared mangano-manganic oxide products.
Embodiment
Battery positive-material lithium manganate of the present invention is used METHODS OF MAKING MANGANIC MANGANOUS OXIDE; Its concrete steps are: with the high pure metal manganese powder with dry milling to certain grain size distribution; In reactor, add blowing air oxidation behind water and the ammonium salt, the initial reaction stage air mass flow is 20 ~ 100 m
3/ h, reaction air mass flow after the 5th hour is adjusted into 40 ~ 300m
3/ h, reaction air mass flow after the 12nd hour is adjusted to 20 ~ 100m
3/ h finishes until reaction, and mixing speed is controlled at 250r/min ~ 450r/min, and the course of reaction required time is 18 ~ 28h, and the reaction end pH value is controlled at 6.4 ± 0.2, after reacting completely, after washing, drying, makes the mangano-manganic oxide product.
Wherein, the particle size distribution after the manganese powder fragmentation is: D10:1.5 μ m ~ 5.8 μ m, D50:6 μ m ~ 30 μ m, D90:30 μ m ~ 50 μ m.
The addition of said ammonium salt is 0.5% ~ 10% of a manganese powder quality.Said ammonium salt is one or more in ammonium chloride, ammonium sulfate, the ammonium nitrate.
Below in conjunction with embodiment the inventive method and products thereof is done further detailed introduction:
Embodiment one
To meta particle diameter 6 μ m ~ 8 μ m, input has added in the reactor of pure water and 80kg ammonium salt (mixture of ammonium chloride and ammonium sulfate) with the dry milling of 1000kg high pure metal manganese powder, and mixing speed is controlled at 360r/min.Blowing air oxidation, initial reaction stage air mass flow are 80 m
3/ h, reaction air mass flow after the 5th hour is adjusted into 200 m
3/ h, reaction air mass flow after the 12nd hour is adjusted to 40 m
3/ h finishes until reaction.Behind the reaction 27h, obtain the mangano-manganic oxide product after the washing of slip process, the drying.
The prepared mangano-manganic oxide product of present embodiment: the meta particle diameter is 27 μ m, and specific area is 1.65m
2/ g, tap density 2.2 g/cm
3
Embodiment two
To meta particle diameter 15 μ m ~ 20 μ m, input has added in the reactor of pure water and 15kg ammonium chloride with the dry milling of 500kg high pure metal manganese powder, and mixing speed is controlled at 280r/min.Blowing air oxidation, initial reaction stage air mass flow are 50 m
3/ h, reaction air mass flow after the 5th hour is adjusted into 150 m
3/ h, reaction air mass flow after the 12nd hour is adjusted to 50 m
3/ h finishes until reaction.After reacting about 20h, obtain the mangano-manganic oxide product after the washing of slip process, the drying.
The prepared mangano-manganic oxide product of present embodiment: the meta particle diameter is 18 μ m, and specific area is 1.24m
2/ g, tap density 2.8 g/cm
3
Embodiment three
To meta particle diameter 25 μ m ~ 30 μ m, input has added in the reactor of pure water and 5kg ammonium nitrate with the dry milling of 100kg high pure metal manganese powder, and mixing speed is controlled at 395r/min.Blowing air oxidation, initial reaction stage air mass flow are 20 m
3/ h, reaction air mass flow after the 5th hour is adjusted into 40 m
3/ h, reaction air mass flow after the 12nd hour is adjusted to 60 m
3/ h finishes until reaction.Behind the reaction 18h, obtain the mangano-manganic oxide product after the washing of slip process, the drying.
The prepared mangano-manganic oxide product of present embodiment: the meta particle diameter is 15 μ m, and specific area is 2.67m
2/ g, tap density 2.6 g/cm
3
Can find out from embodiments of the invention, can control the particle size distribution of final products mangano-manganic oxide through the particle size distribution of controlling manganese powder early stage; Air mass flow influences D10, D50, D90 and the tap density etc. (D50 is meant in the particle 50% particle grain size, just the meta particle diameter of product) of product mangano-manganic oxide.
The special-purpose mangano-manganic oxide of the LiMn2O4 that utilizes the inventive method to obtain, its meta particle diameter is 15 μ m ~ 30 μ m, specific area is 1.0m
2/ g ~ 4.0m
2/ g, tap density is 2.0 g/cm
3~ 3.0g/cm
3Wherein, the Mn content in the mangano-manganic oxide is greater than 71%, and S content is less than 0.03%, and other are impurity.Other impurity comprise any one or more among K, Na, Ca, Fe, Ni, Pb, Cu, Zn, the Cr.
Table 1 is the mangano-manganic oxide that obtains of the inventive method and the performance table of comparisons of common mangano-manganic oxide
Can find out that from table 1 advantage of the product that the inventive method obtains is the meta particle diameter of product high (D50 is higher than existing product), specific area is low, tap density is high.Simultaneously, granule-morphology rule of the present invention, metals content impurity is low.So the manganate cathode material for lithium that this mangano-manganic oxide is produced has good, the characteristics such as compacted density is high, good cycle of volumetric properties.
Claims (7)
1. battery positive-material lithium manganate is used METHODS OF MAKING MANGANIC MANGANOUS OXIDE, and its concrete steps are:
With the high pure metal manganese powder with dry milling to certain grain size distribution, in reactor, add blowing air oxidation behind water and the ammonium salt, the initial reaction stage air mass flow is 20 ~ 100 m
3/ h, reaction air mass flow after the 5th hour is adjusted into 40 ~ 300m
3/ h, reaction air mass flow after the 12nd hour is adjusted to 20 ~ 100m
3/ h finishes until reaction, and mixing speed is controlled at 250r/min ~ 450r/min, and the course of reaction required time is 18 ~ 28h, and the reaction end pH value is controlled at 6.4 ± 0.2, after reacting completely, after washing, drying, makes the mangano-manganic oxide product.
2. preparation method according to claim 1 is characterized in that: the particle size distribution after the manganese powder fragmentation is: D10:1.5 μ m ~ 5.8 μ m, D50:6 μ m ~ 30 μ m, D90:30 μ m ~ 50 μ m.
3. preparation method according to claim 1 is characterized in that: the addition of said ammonium salt is 0.5% ~ 10% of a manganese powder quality.
4. preparation method according to claim 1 is characterized in that: said ammonium salt is one or more in ammonium chloride, ammonium sulfate, the ammonium nitrate.
5. according to the mangano-manganic oxide of claim 1,2,3,4 preparation method's gained, it is characterized in that: the meta particle diameter of mangano-manganic oxide is 15 μ m ~ 30 μ m, and specific area is 1.0m
2/ g ~ 4.0 m
2/ g, tap density is 2.0 g/cm
3~ 3.0g/cm
3
6. according to the mangano-manganic oxide of claim 1,2,3,4 preparation method's gained, it is characterized in that: the Mn content in the mangano-manganic oxide is greater than 71%, and S content is less than 0.03%, and other are impurity.
7. mangano-manganic oxide according to claim 6 is characterized in that: other impurity comprise any one or more among K, Na, Ca, Fe, Ni, Pb, Cu, Zn, the Cr.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104803419A (en) * | 2015-02-28 | 2015-07-29 | 四川中哲新材料科技有限公司 | Preparation method of manganous-manganic oxide |
| CN105948130A (en) * | 2016-07-05 | 2016-09-21 | 湖南蒙达新能源材料有限公司 | Trimanganese tetraoxide, as well as preparation method and application thereof |
| CN107681134A (en) * | 2017-09-07 | 2018-02-09 | 浙江瓦力新能源科技有限公司 | The preparation method of High-performance lithium manganate anode material |
| CN108059190A (en) * | 2017-12-14 | 2018-05-22 | 中钢集团安徽天源科技股份有限公司 | A kind of LiMn2O4 compound mangano-manganic oxide and its industrial production process |
| CN108069459A (en) * | 2017-12-14 | 2018-05-25 | 中钢集团安徽天源科技股份有限公司 | A kind of LiMn2O4 mangano-manganic oxide and its industrial production process |
| CN109052480A (en) * | 2018-09-30 | 2018-12-21 | 贵州铜仁金瑞锰业有限责任公司 | A kind of high-purity mangano-manganic oxide and preparation method thereof |
| CN115676893A (en) * | 2022-11-10 | 2023-02-03 | 焦作伴侣纳米材料工程有限公司 | Composite manganese source for lithium manganate, preparation method of composite manganese source, lithium manganate and application of composite manganese source |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104803419A (en) * | 2015-02-28 | 2015-07-29 | 四川中哲新材料科技有限公司 | Preparation method of manganous-manganic oxide |
| CN105948130A (en) * | 2016-07-05 | 2016-09-21 | 湖南蒙达新能源材料有限公司 | Trimanganese tetraoxide, as well as preparation method and application thereof |
| CN105948130B (en) * | 2016-07-05 | 2017-06-09 | 湖南蒙达新能源材料有限公司 | A kind of mangano-manganic oxide, preparation method and applications |
| CN107681134A (en) * | 2017-09-07 | 2018-02-09 | 浙江瓦力新能源科技有限公司 | The preparation method of High-performance lithium manganate anode material |
| CN108059190A (en) * | 2017-12-14 | 2018-05-22 | 中钢集团安徽天源科技股份有限公司 | A kind of LiMn2O4 compound mangano-manganic oxide and its industrial production process |
| CN108069459A (en) * | 2017-12-14 | 2018-05-25 | 中钢集团安徽天源科技股份有限公司 | A kind of LiMn2O4 mangano-manganic oxide and its industrial production process |
| CN108069459B (en) * | 2017-12-14 | 2019-07-16 | 中钢集团安徽天源科技股份有限公司 | A kind of LiMn2O4 mangano-manganic oxide and its industrial production process |
| CN109052480A (en) * | 2018-09-30 | 2018-12-21 | 贵州铜仁金瑞锰业有限责任公司 | A kind of high-purity mangano-manganic oxide and preparation method thereof |
| CN115676893A (en) * | 2022-11-10 | 2023-02-03 | 焦作伴侣纳米材料工程有限公司 | Composite manganese source for lithium manganate, preparation method of composite manganese source, lithium manganate and application of composite manganese source |
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