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共沉淀条件对无钴LiNiMnAlO正极材料电化学性能的影响

Effects of Coprecipitation Conditions on the Electrochemical Properties of Cobalt-Free LiNiMnAlO Cathodes.

作者信息

Lee Steven, Kmiec Steven, Manthiram Arumugam

机构信息

Materials Science and Engineering Program and Texas Materials Institute, The University of Texas at Austin, Austin, TX, 78712, USA.

出版信息

Small. 2024 Dec;20(50):e2406947. doi: 10.1002/smll.202406947. Epub 2024 Sep 27.

Abstract

Commercializing high-nickel, cobalt-free cathodes, such as LiNiMnAlO (NMA-90), hinges on effectively incorporating Al during the hydroxide coprecipitation reaction. However, Al coprecipitation is nontrivial as Al possesses unique precipitation properties compared to Ni and Mn, which impact the final precursor morphology and consequently the cathode properties. In this study, the nuance of Al coprecipitation and its influence on the cycling stability of NMA with increasing Al content is elucidated. While low reaction pH and ammonia concentration are suitable for producing Al-free LiNiMnO (NM-90) effectively, the same coprecipitation environment leads to porous precursor morphology and poor cycle life in Al-containing LiNiMnAlO (NMA-900802) and LiNiMnAlO (NMA-900505). By systematically increasing the reaction pH and ammonia concentration for the Al-containing compositions, the precursor morphology becomes denser and the cathode cycling stability is greatly improved. It is hypothesized that the improvement in cycling stability stems from the reduction in Al(OH) nucleation, which promotes hydroxide particle growth with optimal Al incorporation into the cathode lattice.

摘要

商业化高镍无钴阴极,如LiNiMnAlO(NMA - 90),取决于在氢氧化物共沉淀反应过程中有效地掺入铝。然而,铝的共沉淀并非易事,因为与镍和锰相比,铝具有独特的沉淀特性,这会影响最终前驱体的形态,进而影响阴极性能。在本研究中,阐明了铝共沉淀的细微差别及其对随着铝含量增加的NMA循环稳定性的影响。虽然低反应pH值和氨浓度适合有效地生产无铝的LiNiMnO(NM - 90),但相同的共沉淀环境会导致含铝的LiNiMnAlO(NMA - 900802)和LiNiMnAlO(NMA - 900505)前驱体形态多孔且循环寿命较差。通过系统地提高含铝组合物的反应pH值和氨浓度,前驱体形态变得更致密,阴极循环稳定性得到极大提高。据推测,循环稳定性的提高源于Al(OH)成核的减少,这促进了氢氧化物颗粒的生长,并使铝以最佳方式掺入阴极晶格。

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