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用于锂离子电池的LiNiMnO正极的钛表面掺杂

Ti surface doping of LiNiMnO positive electrodes for lithium ion batteries.

作者信息

Ulu Okudur F, D'Haen J, Vranken T, De Sloovere D, Verheijen M, Karakulina O M, Abakumov A M, Hadermann J, Van Bael M K, Hardy A

机构信息

UHasselt, Institute for Materials Research (IMO-IMOMEC), Partner in Energyville, Inorganic and Physical Chemistry Agoralaan, 3590 Diepenbeek Belgium

UHasselt, Institute for Materials Research (IMO-IMOMEC), Materials Physics Wetenschapspark 1, 3590 Diepenbeek Belgium.

出版信息

RSC Adv. 2018 Feb 13;8(13):7287-7300. doi: 10.1039/c7ra12932g. eCollection 2018 Feb 9.

DOI:10.1039/c7ra12932g
PMID:35540314
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9078446/
Abstract

The particle surface of LiNiMnO (LNMO), a Li-ion battery cathode material, has been modified by Ti cation doping through a hydrolysis-condensation reaction followed by annealing in oxygen. The effect of different annealing temperatures (500-850 °C) on the Ti distribution and electrochemical performance of the surface modified LNMO was investigated. Ti cations diffuse from the preformed amorphous 'TiO ' layer into the LNMO surface during annealing at 500 °C. This results in a 2-4 nm thick Ti-rich spinel surface having lower Mn and Ni content compared to the core of the LNMO particles, which was observed with scanning transmission electron microscopy coupled with compositional EDX mapping. An increase in the annealing temperature promotes the formation of a Ti bulk doped LiNiMn Ti O phase and Ti-rich LiNiMn Ti O segregates above 750 °C. Fourier-transform infrared spectrometry indicates increasing Ni-Mn ordering with annealing temperature, for both bare and surface modified LNMO. Ti surface modified LNMO annealed at 500 °C shows a superior cyclic stability, coulombic efficiency and rate performance compared to bare LNMO annealed at 500 °C when cycled at 3.4-4.9 V Li/Li. The improvements are probably due to suppressed Ni and Mn dissolution with Ti surface doping.

摘要

锂离子电池正极材料LiNiMnO（LNMO）的颗粒表面通过水解缩合反应进行Ti阳离子掺杂改性，随后在氧气中退火。研究了不同退火温度（500 - 850°C）对表面改性LNMO的Ti分布和电化学性能的影响。在500°C退火过程中，Ti阳离子从预先形成的非晶态“TiO ”层扩散到LNMO表面。这导致形成了一个厚度为2 - 4 nm的富Ti尖晶石表面，与LNMO颗粒的核心相比，其Mn和Ni含量较低，这是通过扫描透射电子显微镜结合能谱EDX映射观察到的。退火温度的升高促进了Ti体掺杂LiNiMnTi O相的形成，并且在750°C以上出现富Ti的LiNiMnTi O偏析物。傅里叶变换红外光谱表明，对于未处理的和表面改性的LNMO，随着退火温度的升高，Ni - Mn有序度增加。当在3.4 - 4.9 V Li/Li下循环时，在500°C退火的Ti表面改性LNMO与在500°C退火的未处理LNMO相比，表现出优异的循环稳定性、库仑效率和倍率性能。这些改进可能是由于Ti表面掺杂抑制了Ni和Mn的溶解。

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