Identifying the redox activity of cation-disordered Li-Fe-V-Ti oxide cathodes for Li-ion batteries

Physical Chemistry Chemical Physics : PCCP
Ruiyong ChenSylvio Indris

Abstract

Cation-disordered oxides have recently shown promising properties on the way to explore high-performance intercalation cathode materials for rechargeable Li-ion batteries. Here, stoichiometric cation-disordered Li2FeVyTi1-yO4 (y = 0, 0.2, 0.5) nanoparticles are studied. The substitution of V for Ti in Li2FeVyTi1-yO4 increases the content of active transition metals (Fe and V) and accordingly the amount of Li(+) (about (1 + y)Li(+) capacity per formula unit) that can be reversibly intercalated. It is found that Fe(3+)/Fe(2+) and V(4+)/V(3+) redox couples contribute to the overall capacity performance, whereas Ti(4+) remains mainly inert. There is no evidence for the presence of Fe(4+) species after charging to 4.8 V, as confirmed from the ex situ(57)Fe Mössbauer spectroscopy and the Fe K-edge absorption spectra. The redox couple reactions for iron and vanadium are examined by performing in situ synchrotron X-ray absorption spectroscopy. During charging/discharging, the spectral evolution of the K-edges for Fe and V confirms the reversible Fe(3+)/Fe(2+) and V(4+)/V(3+) redox reactions during cycling between 1.5 and 4.8 V.

References

Sep 14, 2010·Journal of the American Chemical Society·Shin-ichi NishimuraAtsuo Yamada
Jul 16, 2013·Nature Materials·M SathiyaJ-M Tarascon
May 9, 2014·Scientific Reports·Atsushi SakudaZempachi Ogumi
Nov 29, 2014·Physical Chemistry Chemical Physics : PCCP·Ruiyong ChenSylvio Indris
Jun 10, 2015·Proceedings of the National Academy of Sciences of the United States of America·Naoaki YabuuchiShinichi Komaba
Jun 16, 2015·Physical Chemistry Chemical Physics : PCCP·Ruiyong ChenHorst Hahn

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Citations

Nov 7, 2019·ACS Applied Materials & Interfaces·Meng YangXiaodong Shen
Sep 22, 2020·ACS Applied Energy Materials·Andrew J NaylorDaniel Brandell

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