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The electrochemical reactions of pure In with Li and Na: anomalous electrolyte decomposition, benefits of FEC additive, phase...

by Samantha A Hawks, Loic Baggetto, Craig A Bridges, Gabriel M Veith
Publication Type
Journal
Journal Name
Journal of Power Sources
Publication Date
Page Numbers
1105 to 1117
Volume
248
Issue
1

Indium thin films are evaluated as an anode material for Li-ion and Na-ion batteries (theoretical capacities of 1012 mAh g-1 for Li and 467 mAh g-1 for Na). The native surface oxides are responsible for the anomalous electrolyte decomposition during the first cycle while oxidized In species are found to be responsible for the electrolyte decomposition during the subsequent cycles. The presence of 5wt% FEC electrolyte additive suppresses the occurrence of the anomalous electrolyte decomposition during the first cycle but is not sufficient to prevent the decomposition upon further cycling from 0 to 2 V. Prevention of the anomalous decomposition can be achieved by restricting the charge cut-off, for instance at 1.1 V, or by using larger amounts of FEC. The In films show moderately good capacity retention with storage capacities when cycled with Li (950 mAh g-1) but significantly less when cycled with Na (125 mAh g-1). XRD data reveal that several known Li-In phases (i.e LiIn, Li3In2, LiIn2 and Li13In3) form during the electrochemical reaction. In contrast, the reaction with Na is severely limited. The largest amount of inserted Na is evidenced for cells short-circuited 40 hrs at 65C, for which the XRD data show the coexistence of NaIn, In, and an unknown phase. During cycling, mechanical degradation due to repeated expansion/shrinkage, evidenced by SEM, coupled with SEI formation is the primary source of the capacity fade. Finally, we show that the In thin films exhibit very high rate capability for both Li (100 C) and Na (30 C).