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

Literature Information

Publication Date 2016-02-10
DOI 10.1039/C6CP00131A
Impact Factor 3.676
Authors

Ralf Witte, Ralf Heinzmann, Shuhua Ren, Stefan Mangold, Horst Hahn, Rolf Hempelmann, Helmut Ehrenberg


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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 Fe3+/Fe2+ and V4+/V3+ redox couples contribute to the overall capacity performance, whereas Ti4+ remains mainly inert. There is no evidence for the presence of Fe4+ species after charging to 4.8 V, as confirmed from the ex situ57Fe 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 Fe3+/Fe2+ and V4+/V3+ redox reactions during cycling between 1.5 and 4.8 V.

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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