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Origin of Fracture‐Resistance to Large Volume Change in Cu‐Substituted Co 3 O 4 Electrodes
Author(s) -
Liu Heguang,
Li Qianqian,
Yao Zhenpeng,
Li Lei,
Li Yuan,
Wolverton Chris,
Hersam Mark C.,
Wu Jinsong,
Dravid Vinayak P.
Publication year - 2018
Publication title -
advanced materials
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 10.707
H-Index - 527
eISSN - 1521-4095
pISSN - 0935-9648
DOI - 10.1002/adma.201704851
Subject(s) - materials science , nanoclusters , electrode , metal , copper , volume (thermodynamics) , conductivity , electrical resistivity and conductivity , chemical engineering , chemical physics , nanotechnology , metallurgy , chemistry , thermodynamics , physics , engineering , electrical engineering
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 Co 3 O 4 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 Li 2 O. 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 Li 2 O in the discharge cycle and underpins the catalytic activity of Li 2 O decomposition in the charge cycle.