Revealing the Conversion Mechanism of Transition Metal Oxide Electrodes during Lithiation from First-Principles

Zhenpeng Yao, Soo Kim, Muratahan Aykol, Qianqian Li, Jinsong Wu, Jiangang He, Chris Wolverton*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

52 Scopus citations


Transition metal oxides such as Co3O4 and NiO are of significant interest as conversion anode materials for lithium-ion batteries (LIBs), due to their remarkably high theoretical capacities and low cost. While many previous experiments have found that the charge/discharge reactions of Co3O4 and NiO can be highly reversible, detailed information about the mechanisms of these reactions, such as the origin of the voltage hysteresis (>1.0 V) between the charge/discharge cycles, is still poorly understood. In this work, we develop and utilize a new computational mechanistic approach that helps elucidate the hysteresis and nonequilibrium reaction pathways associated with these conversion materials. We apply this methodology to investigate a variety of lithiation reaction pathways of Co3O4 and NiO by systematically exploring the energetics of a large number of equilibrium and nonequilibrium LixCo3O4 (0 ≤ x ≤ 8) and LixNiO (0 ≤ x ≤ 2) structural configurations using first-principles calculations. The overall value of the voltages from our nonequilibrium pathway is in much better agreement with experimental lithiation than the calculated equilibrium voltage while the overall value of the latter reasonably agrees with experimental delithiation. Hence, we propose the charge and discharge processes proceed through equilibrium and nonequilibrium reaction paths, respectively, which contribute significantly to the experimentally observed voltage hysteresis in Co3O4 and NiO. Additionally, we find a low-energy, lithiated intermediate phase (Li3Co3O4) with an oxygen framework equal to that of the initial Co3O4 spinel phase. This intermediate phase represents the capacity threshold below which limited volume expansion and better reversibility can be realized and above which reactions lead to structural degradation and huge expansion.

Original languageEnglish (US)
Pages (from-to)9011-9022
Number of pages12
JournalChemistry of Materials
Issue number21
StatePublished - Nov 14 2017

ASJC Scopus subject areas

  • General Chemistry
  • General Chemical Engineering
  • Materials Chemistry


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