The electrochemical reactions of pure indium with Li and Na: Anomalous electrolyte decomposition, benefits of FEC additive, phase transitions and electrode performance

Samantha A. Webb, Loïc Baggetto, Craig A. Bridges, Gabriel M. Veith

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96 Scopus citations

Abstract

Indium thin films were 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). XRD data reveal that several known Li-In phases (LiIn, Li3In2, LiIn2 and Li13In 3) form providing 950 mAh g-1 reversible capacity. In contrast, the reaction with Na is severely limited (75-125 mAh g-1). XRD data of short-circuited cells (40 h at 65 C) show the coexistence of NaIn, In, and an unknown NaxIn phase. In electrodes exhibit anomalous electrolyte decomposition characterized by large discharge plateaus at 1.4 V vs Li/Li+ and 0.9 V vs Na/Na+. The presence of 5 wt% fluoroethylene carbonate additive suppresses the occurrence of the electrolyte decomposition during the first cycle but does not necessarily prevent it upon further cycling. Prevention of the anomalous decomposition can be achieved by restricting the (dis)charge voltages, increasing the current or by using larger amounts of FEC. The native surface oxides (In2O3) are responsible for the pronounced electrolyte decomposition during the first cycle while other In3+ species are responsible during the subsequent cycles. We also show that indium electrodes can exhibit very high rate capability for both Li (100 C-rate) and Na (30 C-rate).

Original languageEnglish
Pages (from-to)1105-1117
Number of pages13
JournalJournal of Power Sources
Volume248
DOIs
StatePublished - 2014

Funding

This work was supported by the U.S. Department of Energy (DOE) , Basic Energy Sciences (BES) , Materials Sciences and Engineering Division . Microscopy research was supported via a user project supported by ORNL's Shared Research Equipment (ShaRE) User Program, which is also supported by DOE-BES.

Keywords

  • Anomalous electrolyte decomposition
  • Benefits of fluoroethylene additive (FEC) additive
  • Indium (In) sputtered thin films
  • Lithium-ion anode
  • Sodium-ion anode
  • Very high rate performance

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