Synthesis and electrochemical properties of LiyM1-xCaxMnO3 (M = Pr, Eu) solid solutions

V. Kordan; O. Zaremba; P. Demchenko; V. Pavlyuk

doi:10.15330/pcss.23.4.699-704

Authors

V. Kordan Ivan Franko National University of Lviv, Lviv, Ukraine
O. Zaremba Ivan Franko National University of Lviv, Lviv, Ukraine
P. Demchenko Ivan Franko National University of Lviv, Lviv, Ukraine
V. Pavlyuk Ivan Franko National University of Lviv, Lviv, Ukraine; Jan Długosz University of Czestochowa, Czestochowa, Poland

DOI:

https://doi.org/10.15330/pcss.23.4.699-704

Keywords:

X-ray diffraction, electron microscopy, perovskite structure, electrochemical lithiation

Abstract

New Li-containing solid solutions Li_yM_1-xCa_xMnO₃(M = Pr and Eu) were synthesized by electrochemical lithiation of the ceramics with perovskite structure. The qualitative and quantitative composition of the initial and Li-containing ceramics was determined by scanning electron microscopy and energy-dispersive X-ray spectroscopy. The M/Ca/Mn cation ratio was confirmed by X-ray fluorescence spectroscopy. The crystal structure of theM_1-xCa_xMnO₃solid solutions before lithiation (GdFeO₃-type structure, space group Pnma, Pearson code oP20) and after lithiation (filled-up GdFeO₃-type) was determined by the Rietveld method. X-ray structural analysis showed the formation of phases with increased unit cell parameters after lithiation process. In the case of Eu and Pr-containing samples X-rays diffraction patterns illustrate the amorphous halo based on the by-products of reaction between of ceramics surface and components from electrolyte. Under experimental conditions (Li-metal anode) the quantity of intercalated Li increases for ceramics: Li_0.084Eu_0.5Ca_0.5MnO₃, Li_0.113Pr_0.5Ca_0.5MnO₃, and Li_0.134Pr_0.7Ca_0.3MnO₃. Scanning electron microscopy method revealed the formation of Li-containing aggregates with dimension of 200-900 nm. The grains demonstrate block-like or irregular shape morphology with developed area surface.

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