Origin of Fracture-Resistance to Large Volume Change in Cu-Substituted Co3O4 Electrodes

Heguang Liu, Qianqian Li, Zhenpeng Yao, Lei Li, Yuan Li, Chris Wolverton, Mark C. Hersam, Jinsong Wu, Vinayak P. Dravid

Research output: Contribution to journalArticle

17 Citations (Scopus)

Abstract

The electrode materials conducive to conversion reactions undergo large volume change in cycles which restrict their further development. It has been demonstrated that incorporation of a third element into metal oxides can improve the cycling stability while the mechanism remains unknown. Here, an in situ and ex situ electron microscopy investigation of structural evolutions of Cu-substituted Co3O4 supplemented by first-principles calculations is reported to reveal the mechanism. An interconnected framework of ultrathin metallic copper formed provides a high conductivity backbone and cohesive support to accommodate the volume change and has a cube-on-cube orientation relationship with Li2O. In charge, a portion of Cu metal is oxidized to CuO, which maintains a cube-on-cube orientation relationship with Cu. The Co metal and oxides remain as nanoclusters (less than 5 nm) thus active in subsequent cycles. This adaptive architecture accommodates the formation of Li2O in the discharge cycle and underpins the catalytic activity of Li2O decomposition in the charge cycle.

Original languageEnglish
Article number1704851
JournalAdvanced Materials
Volume30
Issue number4
DOIs
Publication statusPublished - Jan 25 2018

Keywords

  • Cu-doping transition metal oxides
  • cycling stability
  • in situ transmission electron microscopy (TEM)
  • lithium-ion batteries

ASJC Scopus subject areas

  • Materials Science(all)
  • Mechanics of Materials
  • Mechanical Engineering

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    Liu, H., Li, Q., Yao, Z., Li, L., Li, Y., Wolverton, C., Hersam, M. C., Wu, J., & Dravid, V. P. (2018). Origin of Fracture-Resistance to Large Volume Change in Cu-Substituted Co3O4 Electrodes. Advanced Materials, 30(4), [1704851]. https://doi.org/10.1002/adma.201704851