Journal
ELECTROCHIMICA ACTA
Volume 263, Issue -, Pages 533-543Publisher
PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.electacta.2018.01.087
Keywords
LiZr2(PO4)(3); Sol-gel synthesis; Solid electrolytes; Raman spectroscopy; Impedance spectroscopy
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Funding
- Department of Science & Technology (DST), Govt. of India under INSPIRE Faculty scheme
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Effects of Al3+ substitution for Zr4+ in LiZr2(PO4)(3) on its structure and lithium ion conduction are investigated. Li1+xZr2-xAlx(PO4)(3) samples prepared via a sol-gel route and calcined at 900 degrees C crystallize in monoclinic structure with P2(1)/n space group and show a reduction in cell volume with an increase in x. Raman spectra showed an increase in broadening of higher frequency v(1) & v(3) vibrational modes and a spectral weight transfer between v(2) & v(4) bending modes of PO4 tetrahedra with the increase in Al3+ doping. Analysis of Raman spectra further suggested that the renormalization of the mode frequencies in doped samples is controlled by Li-ion motion via strongly interacting with internal bending modes of PO4 tetrahedra. A significant improvement in ionic conductivity was observed in Al-doped samples, and the highest conductivity of 1.83 x 10(-4) Omega(-1)m(-1) and lithium diffusion coefficient of about 5.7 x 10(-19) m(2)s(-1) was observed for Li1.25Zr1.75Al0.25(PO4)(3) at room temperature. Li transference number suggested that the conductivity in Li1.25Zr1.75Al0.25(PO4)(3) is predominantly ionic. Activation energy was found to decrease from 0.58 eV for LiZr2(PO4)(3) to 0.47 eV for Li1.25Zr1.75Al0.25(PO4)(3). (c) 2018 Elsevier Ltd. All rights reserved.
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