期刊
JOURNAL OF POWER SOURCES
卷 298, 期 -, 页码 363-368出版社
ELSEVIER
DOI: 10.1016/j.jpowsour.2015.08.062
关键词
In situ X-ray diffraction; LiFeSO4F; Reaction mechanism
资金
- Swedish Governmental Agency for Innovation Systems (Vinnova) [P37446-1]
- Swedish Energy Agency [30769-2]
- Swedish Research Council [C0468101]
- Angstrom Advanced Battery Centre [2012-4681]
- STandUp-strategic research program
The tavorite-type polymorph of LiFeSO4F has recently attracted substantial attention as a positive electrode material for lithium ion batteries. The synthesis of this material is generally considered to rely on a topotactic exchange of water (H2O) for lithium (Li) and fluorine (F) within the structurally similar hydrated iron sulfate precursor (FeSO4 center dot H2O) when reacted with lithium fluoride (LiF). However, there have also been discussions in the literature regarding the possibility of a non-topotactic reaction mechanism between lithium sulfate (Li2SO4) and iron fluoride (FeF2) in tetraethylene glycol (TEG) as reaction medium. In this work, we use in situ X-ray diffraction to continuously follow the formation of LiFeSO4F from the two suggested precursor mixtures in a setup aimed to mimic the conditions of a solvothermal autoclave synthesis. It is demonstrated that LiFeSO4F is formed directly from FeSO4 center dot H2O and LiF, in agreement with the proposed topotactic mechanism. The Li2SO4 and FeF2 precursors, on the other hand, are shown to rapidly transform into FeSO4 center dot H2O and LiF with the water originating from the highly hygroscopic TEG before a subsequent formation of LiFeSO4F is initiated. The results highlight the importance of the FeSO4 center dot H2O precursor in obtaining the tavorite-type LiFeSO4F, as it is observed in both reaction routes. (C) 2015 Elsevier B.V. All rights reserved.
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