NDLI: Lithium metal fluorosulfate polymorphs as positive electrodes for Li-ion batteries: synthetic strategies and effect of cation ordering

Content Provider	Royal Society of Chemistry (RSC)
Author	Ellis, Brian L. Huq, Ashfia Nazar, L. F. Tripathi, Rajesh Popov, Guerman
Copyright Year	2012
Abstract	Transition-metal fluorosulfates are currently being extensively explored for their use as cathodes in Li-ion batteries. Several new polymorphs of LiMSO4F (M = Fe, Mn, Zn) crystallizing in the tavorite, triplite and sillimanite structures have captured much recent interest, but synthetic access is limited and the underlying phase stability and ion transport in these materials are poorly understood. Here we report that solvothermal routes to LiMSO4F (M = Fe, Mn, Zn) offer significant advantage over both exotic ionothermal methods and solid state synthesis by enabling greater control of the chemistry. We show new limits for the onset of triplite crystallization, and report new phases in the Li[Fe,Zn]SO4F system that enable a fuller understanding of the complex chemistry and thermodynamics underlying these fascinating materials. The transformation of LiFeSO4F from the tavorite to the triplite polymorph is triggered in the absence of any substituents, proving that tavorite is an intermediate in the reaction pathway. As a result of structural changes between tavorite and triplite, their Li+ transport paths are quite different. Combined X-ray/neutron diffraction studies of the triplites suggest that distinct inter-site zig-zag paths must be involved, owing to complete cation disorder that impacts the electrochemical behavior.
Starting Page	6238
Ending Page	6246
Page Count	9
File Format	HTM / HTML PDF
ISSN	17545692
Volume Number	5
Issue Number	3
Journal	Energy & Environmental Science
DOI	10.1039/c2ee03222h
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Granulocyte Triplite Sillimanite Ion Shapeshifting X-ray crystallography Neutron diffraction Electrochemistry
Content Type	Text
Resource Type	Article
Subject	Environmental Chemistry Pollution Renewable Energy, Sustainability and the Environment Nuclear Energy and Engineering

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