Bulk-phase doped manganous-manganic oxide as well as preparation method and application thereof

A technology of trimanganese tetraoxide and doping, which is applied in the direction of manganese oxide/manganese hydroxide, electrochemical generators, active material electrodes, etc., and can solve the problem of inability to uniformly disperse doping elements, reduce battery product capacity, and high-temperature cycle Poor performance and other problems, to achieve the effect of improving high temperature performance and cycle performance, low production cost, and improving compaction density

Pending Publication Date: 2021-02-23
GUIZHOU DALONG HUICHENG NEW MATERIAL CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, most of the existing technologies adopt mechanical mixing methods, that is, when synthesizing lithium manganate, MMO is mechanically mixed with lithium sources and dopants, and then roasted at high temperature. This method can modify lithium manganate, but due to the doping Impurities are generally lower than 3% relative to the main material, and the doping elements cannot be uniformly dispersed in the material. From a microscopic point of view, the material particles close to the dopant are doped, while the material particles far away from the dopant are not doped. Some doping sources even independently form residual particles, which seriously affect the effect of doping
[0006] Chinese patent CN102491422B disclo

Method used

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  • Bulk-phase doped manganous-manganic oxide as well as preparation method and application thereof
  • Bulk-phase doped manganous-manganic oxide as well as preparation method and application thereof
  • Bulk-phase doped manganous-manganic oxide as well as preparation method and application thereof

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Embodiment 1

[0033] A bulk phase doped trimanganese tetroxide of the present invention, the bulk phase doped trimanganese tetraoxide is doped with ytterbium and niobium, the content of ytterbium is 0.39%, and the content of niobium is 0.14%; the bulk phase doped Type manganese tetraoxide D50 particle size is 8.6μm, tap density is 1.9g / cm 3 .

[0034] The preparation method of the bulk phase doped trimanganese tetraoxide of the present embodiment comprises the following steps:

[0035] (1) Prepare Mn with manganese sulfate and ytterbium sulfate 2+ The concentration is 80g / L, Yb 3+ Concentration is the mixed solution of 0.55g / L, is the soluble niobium solution of 0.18g / L with niobium pentoxide dissolved with sulfuric acid under the aid of ammonium fluoride to form niobium content;

[0036] (2) preparation concentration is the ammonia solution of 80g / L;

[0037] (3) Add the mixed solution prepared by step (1), soluble niobium solution and the ammonia solution of step (2) continuously with...

Embodiment 2

[0041] A bulk phase doped trimanganese tetroxide of the present invention, the bulk phase doped trimanganese tetraoxide is doped with ytterbium and lanthanum; wherein, the content of ytterbium is 0.38%, and the content of lanthanum is 0.23%, the bulk phase Doped trimanganese tetraoxide D50 particle size is 7.1μm, tap density is 2.1g / cm 3 .

[0042] The preparation method of the bulk phase doped trimanganese tetraoxide of the present embodiment comprises the following steps:

[0043] (1) Prepare Mn with manganese sulfate, ytterbium sulfate and lanthanum sulfate 2+ The concentration is 80g / L, Yb 3+ The concentration is 0.55g / L, La 2+ A mixed solution with a concentration of 0.3g / L;

[0044] (2) preparation concentration is the ammonia solution of 100g / L;

[0045] (3) With a peristaltic pump, the mixed solution prepared in step (1) and the aqueous ammonia solution in step (2) are continuously added to a volume of 20L in a stirred reactor, and the temperature of the control r...

Embodiment 3

[0049] A bulk phase doped trimanganese tetroxide of the present invention, the bulk phase doped trimanganese tetroxide is doped with yttrium and lanthanum; wherein, the content of yttrium is 0.35%, and the content of lanthanum is 0.48%, the bulk phase Doped trimanganese tetraoxide D50 particle size is 9.5μm, tap density is 2.0g / cm 3 .

[0050] The preparation method of the bulk phase doped trimanganese tetraoxide of the present embodiment comprises the following steps:

[0051] (1) Prepare Mn with manganese sulfate, yttrium sulfate and lanthanum sulfate 2+ The concentration is 100g / L, Y 3+ The concentration is 0.7g / L, La 3+ A mixed solution with a concentration of 0.75g / L;

[0052] (2) preparation concentration is the ammonia solution of 150g / L;

[0053] (3) With a peristaltic pump, the mixed solution prepared in step (1) and the aqueous ammonia solution in step (2) are continuously added to a volume of 20L in a stirred reactor, and the temperature of the control reaction...

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Abstract

The invention discloses bulk-phase doped manganous-manganic oxide. The bulk-phase doped manganous-manganic oxide is doped with at least one element of yttrium, ytterbium, lanthanum and niobium, wherein the doping amount of the doping element is 0.1%-1.0%, the particle size D50 of manganous-manganic oxide is 3-20 microns, and the tap density is greater than or equal to 1.5 g/cm<3>. The preparationmethod comprises the steps: under a stirring condition, continuously adding a divalent manganese salt and a soluble doped salt solution and ammonia water into a reactor to carry out a coprecipitationreaction, and adding an oxidant to carry out oxidation treatment, so as to obtain the bulk-phase doped manganous-manganic oxide. The manganous-manganic oxide or the manganous-manganic oxide prepared by the preparation method is used as a precursor and mixed with a lithium source, and the mixture is roasted to obtain a lithium ion battery positive electrode material lithium manganate. In the manganous-manganic oxide disclosed by the invention, the doping elements are in uniform bulk phase distribution in microcosmic particles, so that the gram volume of lithium manganate can be improved, the compaction density of the lithium manganate can be improved, and the high-temperature performance and the cycle performance of a lithium manganate product can be remarkably improved.

Description

technical field [0001] The invention belongs to the field of positive electrode materials for lithium ion batteries, and relates to a bulk doped trimanganese tetroxide and a preparation method and application thereof. Background technique [0002] Lithium manganese oxide has a wide application space in lithium-ion batteries, especially small power batteries and energy storage products, due to its rich manganese resources, low price, good safety performance, low temperature and excellent rate performance. [0003] The preparation method of lithium manganate is generally prepared by using electrolytic manganese dioxide (EMD) as the manganese source and lithium carbonate as the lithium source, after mixing, roasting at a high temperature of 700-800°C. [0004] In recent years, the capacity, cycle life, high temperature performance, and safety performance of lithium manganese oxide prepared by using trimanganese tetroxide (MMO) as a manganese source have been significantly impro...

Claims

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Application Information

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IPC IPC(8): C01G45/02H01M4/505H01M10/0525
CPCC01G45/02H01M4/505H01M10/0525H01M2004/028H01M2004/021C01P2004/03C01P2004/61Y02E60/10
Inventor 谌红玉管晓东李达飞黄亚君高智曾昭华申喜元刘务华
Owner GUIZHOU DALONG HUICHENG NEW MATERIAL CO LTD
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