Trace level doping of lithium-rich cathode materials

By Lengyel, Miklos and Shen, Kuan-Yu and Lanigan, Deanna M. and Martin, Jonathan M. and Zhang, Xiaofeng and Axelbaum, Richard L.
Published in J. Mater. Chem. A The Royal Society of Chemistry 2016

Abstract

Lithium ion batteries have revolutionized portable electronics and have the potential to electrify the transportation sector. Lithium-rich cathode materials with the composition xLi2MnO3[middle dot](1-x)Li(Ni1/3Mn1/3Co1/3)O2 have received considerable attention as candidates for Plug-in Hybrid Electric Vehicles (PHEVs) and Electric Vehicles (EVs). Cathodes made from these materials display high capacity (>200 mAhg-1) and good cycling stability, offering twice the energy density of currently available intercalation materials. Unfortunately, their performance is plagued by voltage fade due to a layered-spinel phase transformation. Herein, using spray pyrolysis, we show that certain inexpensive trace level ([less-than-or-equal]1%) dopants can help in mitigating voltage fade, when the material is cycled between 2.0-4.6 V. The dopants lead to greater capacity loss than what would be expected from a capacity that is strictly based on a change in the transitional-metal oxidation state. The results imply that a portion of the capacity of these materials comes from reversible oxygen chemistry. These findings could put a different perspective on fade mechanism prevention.

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