Integrated Nano-Domains of Disordered and Ordered Spinel Phases in LiNi0.5Mn1.5O4 for Li-Ion Batteries
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- 作者：Jung-Hyun Kim ; Ashfia Huq ; Miaofang Chi ; Nicholas P.W. Pieczonka ; Eunseok Lee ; Craig A. Bridges ; Misle M. Tessema ; Arumugam Manthiram ; Kristin A. Persson ; Bob R. Powell
- 刊名：Chemistry of Materials
- 出版年：2014
- 出版时间：August 12, 2014
- 年：2014
- 卷：26
- 期：15
- 页码：4377-4386
- 全文大小：626K
- ISSN：1520-5002
文摘
Recent calculations and experimental data suggest that understanding the local ordering behavior of Ni/Mn will be critical to optimize the electrochemical properties of LiNi0.5Mn1.5O4 (LNMO) high voltage spinel. In this study, we systematically controlled the evolution of Ni and Mn ordering in LNMO samples by annealing them at 700 掳C in air for different dwelling times, followed by quenching to room temperature. The long- and short-range ordering behavior of Ni and Mn were analyzed by combining neutron powder diffraction, X-ray powder diffraction (XRD), transmission electron microscopy (TEM), and Fourier transform infrared spectroscopy (FT-IR) data. The results show that the fraction of ordered phase increases rapidly during initial annealing at 700 掳C for 6 h, and accompanied by decreasing amounts of secondary phases. Annealing longer than 6 h led to the growth in size of ordered domains (i.e., increased segregation of ordered and disordered domains) along with a slow increase in the fraction of ordered phase. The dependence of open circuit voltages (OCVs) of the LNMO on the degree of ordering agrees well with recent calculations using the density functional theory. The increase in the degree of ordering increases the open circuit voltage (OCV) and the initial capacity but reduces cycle life and rate capability. The LNMO delivered optimal battery performances (capacity, cycle life, and rate capability) after annealing at 700 掳C for 2 h. This partially ordered sample showed the respective advantages from both disordered and ordered spinels: better spinel-phase purity (thus, higher initial capacity) from the ordered LNMO and better cycle life and rate capability from the disordered LNMO.