Correlating hysteresis and voltage fade in lithium- and manganese-rich layered transition-metal oxide electrodes

Kevin G. Gallagher, Jason R. Croy, Mahalingam Balasubramanian, Martin Bettge, Daniel P. Abraham, Anthony K. Burrell, Michael M. Thackeray

Research output: Contribution to journalArticlepeer-review

195 Scopus citations

Abstract

Electrochemical studies demonstrate a strong correlation between the phenomena of hysteresis and voltage fade in lithium- and manganese-rich layered transition-metal oxide electrodes. A mechanism is proposed that entails both the reversible and irreversible migration of transition metal ions. Their reversible migration to a metastable configuration, suggested to involve the occupation of tetrahedral sites in the lithium layer, is manifested as a 1 V hysteresis in site energy for 10-15% of the lithium content. The irreversible migration of the transition metal ions through the metastable 'hysteresis' sites to localized and lower energy cubic environments results in the observed voltage fade phenomenon.

Original languageEnglish
Pages (from-to)96-98
Number of pages3
JournalElectrochemistry Communications
Volume33
DOIs
StatePublished - 2013

Funding

Support from the Vehicle Technologies Program , Hybrid and Electric Systems , in particular David Howell, Peter Faguy, and Tien Duong at the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, is gratefully acknowledged. The submitted manuscript has been created by UChicago Argonne, LLC, Operator of Argonne National Laboratory (“Argonne”). Argonne, a U.S. Department of Energy Office of Science Laboratory, is operated under Contract No. DE-AC02-06CH11357. The U.S. Government retains for itself, and others acting on its behalf, a paid-up nonexclusive, irrevocable worldwide license in said article to reproduce, prepare derivative works, distribute copies to the public, and perform publicly and display publicly, by or on behalf of the Government.

Keywords

  • Cathode
  • Decay mechanism
  • Destabilization
  • Intercalation
  • Lithium-ion
  • Tetrahedral site

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