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 language | English |
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Article number | 1704851 |
Journal | Advanced Materials |
Volume | 30 |
Issue number | 4 |
DOIs | |
Publication status | Published - Jan 25 2018 |
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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
Cite this
Origin of Fracture-Resistance to Large Volume Change in Cu-Substituted Co3O4 Electrodes. / Liu, Heguang; Li, Qianqian; Yao, Zhenpeng; Li, Lei; Li, Yuan; Wolverton, Chris; Hersam, Mark C; Wu, Jinsong; Dravid, Vinayak P.
In: Advanced Materials, Vol. 30, No. 4, 1704851, 25.01.2018.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Origin of Fracture-Resistance to Large Volume Change in Cu-Substituted Co3O4 Electrodes
AU - Liu, Heguang
AU - Li, Qianqian
AU - Yao, Zhenpeng
AU - Li, Lei
AU - Li, Yuan
AU - Wolverton, Chris
AU - Hersam, Mark C
AU - Wu, Jinsong
AU - Dravid, Vinayak P.
PY - 2018/1/25
Y1 - 2018/1/25
N2 - 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.
AB - 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.
KW - Cu-doping transition metal oxides
KW - cycling stability
KW - in situ transmission electron microscopy (TEM)
KW - lithium-ion batteries
UR - http://www.scopus.com/inward/record.url?scp=85034116979&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85034116979&partnerID=8YFLogxK
U2 - 10.1002/adma.201704851
DO - 10.1002/adma.201704851
M3 - Article
AN - SCOPUS:85034116979
VL - 30
JO - Advanced Materials
JF - Advanced Materials
SN - 0935-9648
IS - 4
M1 - 1704851
ER -