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 |
|---|---|
| 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
VL - 30
JO - Advanced Materials
JF - Advanced Materials
SN - 0935-9648
IS - 4
M1 - 1704851
ER -