Origin of Fracture-Resistance to Large Volume Change in Cu-Substituted Co3O4 Electrodes
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 in this work, 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. Finally, this adaptive architecture accommodates the formation of Li2O in the discharge cycle and underpins the catalytic activity of Li2O decomposition in the charge cycle.
- Authors:
-
[2];
- Northwestern Univ., Evanston, IL (United States); Xi'an Univ. of Technology (China)
- Northwestern Univ., Evanston, IL (United States)
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Center for Electrical Energy Storage (CEES)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR)
- OSTI Identifier:
- 1470177
- Alternate Identifier(s):
- OSTI ID: 1412574
- Grant/Contract Number:
- AC02-06CH11357; AC02‐05CH11231; NSF NNCI-1542205; NSF DMR-1720139; AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Advanced Materials
- Additional Journal Information:
- Journal Volume: 30; Journal Issue: 4; Related Information: CEES partners with Argonne National Laboratory (lead); University of Illinois, Urbana-Champaign; Northwest University; Journal ID: ISSN 0935-9648
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 25 ENERGY STORAGE; energy storage (including batteries and capacitors); charge transport; materials and chemistry by design; synthesis (novel materials); Cu-doping transition metal oxides; cycling stability; in situ transmission electron microscopy (TEM); lithium‐ion batteries
Citation Formats
Liu, Heguang, Li, Qianqian, Yao, Zhenpeng, Li, Lei, Li, Yuan, Wolverton, Chris, Hersam, Mark C., Wu, Jinsong, and Dravid, Vinayak P. Origin of Fracture-Resistance to Large Volume Change in Cu-Substituted Co3O4 Electrodes. United States: N. p., 2017.
Web. doi:10.1002/adma.201704851.
Liu, Heguang, Li, Qianqian, Yao, Zhenpeng, Li, Lei, Li, Yuan, Wolverton, Chris, Hersam, Mark C., Wu, Jinsong, & Dravid, Vinayak P. Origin of Fracture-Resistance to Large Volume Change in Cu-Substituted Co3O4 Electrodes. United States. https://doi.org/10.1002/adma.201704851
Liu, Heguang, Li, Qianqian, Yao, Zhenpeng, Li, Lei, Li, Yuan, Wolverton, Chris, Hersam, Mark C., Wu, Jinsong, and Dravid, Vinayak P. Wed .
"Origin of Fracture-Resistance to Large Volume Change in Cu-Substituted Co3O4 Electrodes". United States. https://doi.org/10.1002/adma.201704851. https://www.osti.gov/servlets/purl/1470177.
@article{osti_1470177,
title = {Origin of Fracture-Resistance to Large Volume Change in Cu-Substituted Co3O4 Electrodes},
author = {Liu, Heguang and Li, Qianqian and Yao, Zhenpeng and Li, Lei and Li, Yuan and Wolverton, Chris and Hersam, Mark C. and Wu, Jinsong and Dravid, Vinayak P.},
abstractNote = {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 in this work, 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. Finally, this adaptive architecture accommodates the formation of Li2O in the discharge cycle and underpins the catalytic activity of Li2O decomposition in the charge cycle.},
doi = {10.1002/adma.201704851},
journal = {Advanced Materials},
number = 4,
volume = 30,
place = {United States},
year = {Wed Dec 06 00:00:00 EST 2017},
month = {Wed Dec 06 00:00:00 EST 2017}
}
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