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Peculiarities of structure, morphology, and electrochemistry of the doped 5-V spinel cathode materials LiNi0.5-x Mn1.5-y M 详细信息    查看全文
  • 作者：N. V. Kosova ; I. A. Bobrikov ; O. A. Podgornova…
  • 关键词：Doped LiNi0.5Mn1.5O4 ; Mechanical activation ; NPD ; HRTEM ; Electrochemical cycling ; GITT
  • 刊名：Journal of Solid State Electrochemistry
  • 出版年：2016
  • 出版时间：January 2016
  • 年：2016
  • 卷：20
  • 期：1
  • 页码：235-246
  • 全文大小：6,974 KB
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  • 作者单位：N. V. Kosova (1)
    I. A. Bobrikov (2)
    O. A. Podgornova (1)
    A. M. Balagurov (2)
    A. K. Gutakovskii (3) (4)

    1. Institute of Solid State Chemistry and Mechanochemistry SB RAS, 18 Kutateladze, Novosibirsk, Russia, 630128
    2. Joint Institute for Nuclear Research, 6 Joliot-Curie, Dubna, Russia, 141980
    3. Rzhanov Institute of Semiconductor Physics SB RAS, 13 pr. Acad. Lavrent’ev, Novosibirsk, Russia, 630090
    4. Novosibirsk State University, 2 Pirogova, Novosibirsk, Russia, 630090
  • 刊物类别：Chemistry and Materials Science
  • 刊物主题：Chemistry
    Physical Chemistry
    Analytical Chemistry
    Industrial Chemistry and Chemical Engineering
    Characterization and Evaluation Materials
    Condensed Matter
    Electronic and Computer Engineering
  • 出版者：Springer Berlin / Heidelberg
  • ISSN：1433-0768
文摘
The pure LiNi0.5Mn1.5O4 and doped spinels LiNi0.5-x Mn1.5-y M x+y O4 (M = Co, Cr, Ti; x + y = 0.05) were prepared by mechanochemically assisted solid state synthesis using a high-energy AGO-2 planetary mill. The activated samples were annealed at 700 and 800 °C in oxygen and then characterized by x-ray powder diffraction (XRD) and neutron powder diffraction (NPD) with Rietveld refinement, high-resolution transmission electron microscopy (HRTEM) and electron microdiffraction, Fourier transform infrared spectroscopy (FTIR), galvanostatic cycling and galvanostatic intermittent titration technique (GITT). The structure of the high-temperature (HT) samples (800 °C) is well refined with the single Fd-3m spinel. On the contrary, the low-temperature (LT) samples (700 °C) are two-phase spinels with the 5–10 % fraction of the P4332 phase depending on the substitution ion. The dopants preferably substitute for Ni ions that correlates with the appearance of the Li y Ni1-y O by-product (3–7 %). The rock salt-structured phase was observed on the surface of the particles coherently conjugated with the LT spinel crystal bulk. For all doped samples, two pairs of redox peaks are observed on the dQ/dV plots revealing the prevalence of the disordered spinel phase. However, the separation between the peaks increases for the HT samples resulting in better charge-discharge performance as compared with the undoped spinel. Lithium diffusion coefficient (D Li+) of the doped HT spinels estimated by GITT is two orders of magnitude higher than that of the undoped spinel. The highest rate capability is observed for the Ti-doped HT spinel due to larger lattice parameter.

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