skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: 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:
 [1]; ORCiD logo [2];  [2];  [2];  [2];  [2];  [2];  [2];  [2]
  1. Northwestern Univ., Evanston, IL (United States); Xi'an Univ. of Technology (China)
  2. 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) (SC-22); USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR) (SC-21)
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. doi: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. doi: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 = {2017},
month = {12}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 10 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

High rate capabilities Fe3O4-based Cu nano-architectured electrodes for lithium-ion battery applications
journal, June 2006

  • Taberna, P. L.; Mitra, S.; Poizot, P.
  • Nature Materials, Vol. 5, Issue 7, p. 567-573
  • DOI: 10.1038/nmat1672

Ternary Spinel MCo 2 O 4 (M = Mn, Fe, Ni, and Zn) Porous Nanorods as Bifunctional Cathode Materials for Lithium–O 2 Batteries
journal, May 2015

  • Mohamed, Saad Gomaa; Tsai, Yuan-Quei; Chen, Chih-Jung
  • ACS Applied Materials & Interfaces, Vol. 7, Issue 22
  • DOI: 10.1021/acsami.5b02180

Graphene-Wrapped Sulfur Particles as a Rechargeable Lithium–Sulfur Battery Cathode Material with High Capacity and Cycling Stability
journal, July 2011

  • Wang, Hailiang; Yang, Yuan; Liang, Yongye
  • Nano Letters, Vol. 11, Issue 7, p. 2644-2647
  • DOI: 10.1021/nl200658a

Projector augmented-wave method
journal, December 1994


A New Class of Lithium and Sodium Rechargeable Batteries Based on Selenium and Selenium–Sulfur as a Positive Electrode
journal, February 2012

  • Abouimrane, Ali; Dambournet, Damien; Chapman, Karena W.
  • Journal of the American Chemical Society, Vol. 134, Issue 10
  • DOI: 10.1021/ja211766q

Hierarchical Mesoporous 3D Flower-like CuCo2O4/NF for High-Performance Electrochemical Energy Storage
journal, August 2016

  • Jadhav, Harsharaj S.; Pawar, Sambhaji M.; Jadhav, Arvind H.
  • Scientific Reports, Vol. 6, Issue 1
  • DOI: 10.1038/srep31120

In situ atomic-scale imaging of electrochemical lithiation in silicon
journal, October 2012

  • Liu, Xiao Hua; Wang, Jiang Wei; Huang, Shan
  • Nature Nanotechnology, Vol. 7, Issue 11
  • DOI: 10.1038/nnano.2012.170

MoS 2 Nanoplates Consisting of Disordered Graphene-like Layers for High Rate Lithium Battery Anode Materials
journal, November 2011

  • Hwang, Haesuk; Kim, Hyejung; Cho, Jaephil
  • Nano Letters, Vol. 11, Issue 11
  • DOI: 10.1021/nl202675f

Tracking lithium transport and electrochemical reactions in nanoparticles
journal, January 2012

  • Wang, Feng; Yu, Hui-Chia; Chen, Min-Hua
  • Nature Communications, Vol. 3, Issue 1
  • DOI: 10.1038/ncomms2185

Facile synthesis of spinel CuCo 2 O 4 nanocrystals as high-performance cathode catalysts for rechargeable Li–air batteries
journal, January 2014

  • Liu, Ying; Cao, Lu-Jie; Cao, Chen-Wei
  • Chem. Commun., Vol. 50, Issue 93
  • DOI: 10.1039/C4CC04682J

Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study
journal, January 1998

  • Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y.
  • Physical Review B, Vol. 57, Issue 3, p. 1505-1509
  • DOI: 10.1103/PhysRevB.57.1505

In Situ Observation of the Electrochemical Lithiation of a Single SnO2 Nanowire Electrode
journal, December 2010


Comprehensive Enhancement of Nanostructured Lithium-Ion Battery Cathode Materials via Conformal Graphene Dispersion
journal, March 2017


Atomic Resolution Study of Reversible Conversion Reaction in Metal Oxide Electrodes for Lithium-Ion Battery
journal, October 2014

  • Luo, Langli; Wu, Jinsong; Xu, Junming
  • ACS Nano, Vol. 8, Issue 11
  • DOI: 10.1021/nn504806h

Kinetically-Driven Phase Transformation during Lithiation in Copper Sulfide Nanoflakes
journal, August 2017


Self-Templated Formation of Uniform NiCo 2 O 4 Hollow Spheres with Complex Interior Structures for Lithium-Ion Batteries and Supercapacitors
journal, December 2014

  • Shen, Laifa; Yu, Le; Yu, Xin-Yao
  • Angewandte Chemie International Edition, Vol. 54, Issue 6
  • DOI: 10.1002/anie.201409776

Ab initiomolecular dynamics for liquid metals
journal, January 1993


Lithium recycling behaviour of nano-phase-CuCo2O4 as anode for lithium-ion batteries
journal, November 2007


Growth of ultrafine CuCo2O4 nanoparticle on graphene with enhanced lithium storage properties
journal, April 2017


Nano-sized transition-metal oxides as negative-electrode materials for lithium-ion batteries
journal, September 2000

  • Poizot, P.; Laruelle, S.; Grugeon, S.
  • Nature, Vol. 407, Issue 6803, p. 496-499
  • DOI: 10.1038/35035045

Lithium insertion into Co3O4: A preliminary investigation
journal, September 1985


NiCo 2 O 4 Spinel:  First Report on a Transition Metal Oxide for the Negative Electrode of Sodium-Ion Batteries
journal, July 2002

  • Alcántara, R.; Jaraba, M.; Lavela, P.
  • Chemistry of Materials, Vol. 14, Issue 7
  • DOI: 10.1021/cm025556v

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


All-Solid Lithium Electrodes with Mixed-Conductor Matrix
journal, January 1981

  • Boukamp, B. A.
  • Journal of The Electrochemical Society, Vol. 128, Issue 4
  • DOI: 10.1149/1.2127495

Electrochemistry of Selenium with Sodium and Lithium: Kinetics and Reaction Mechanism
journal, August 2016


In Situ TEM of Two-Phase Lithiation of Amorphous Silicon Nanospheres
journal, January 2013

  • McDowell, Matthew T.; Lee, Seok Woo; Harris, Justin T.
  • Nano Letters, Vol. 13, Issue 2
  • DOI: 10.1021/nl3044508

In situ TEM electrochemistry of anode materials in lithium ion batteries
journal, January 2011

  • Liu, Xiao Hua; Huang, Jian Yu
  • Energy & Environmental Science, Vol. 4, Issue 10
  • DOI: 10.1039/c1ee01918j

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


In Situ TEM Observation of the Electrochemical Process of Individual CeO 2 /Graphene Anode for Lithium Ion Battery
journal, February 2013

  • Su, Qingmei; Chang, Ling; Zhang, Jun
  • The Journal of Physical Chemistry C, Vol. 117, Issue 8
  • DOI: 10.1021/jp312169j

Improved Graphite Anode for Lithium-Ion Batteries Chemically
journal, January 1996

  • Peled, E.
  • Journal of The Electrochemical Society, Vol. 143, Issue 1
  • DOI: 10.1149/1.1836372

Li-Storage via Heterogeneous Reaction in Selected Binary Metal Fluorides and Oxides
journal, January 2004

  • Li, Hong; Balaya, Palani; Maier, Joachim
  • Journal of The Electrochemical Society, Vol. 151, Issue 11, p. A1878-A1885
  • DOI: 10.1149/1.1801451

Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium
journal, May 1994


Porous CuCo 2 O 4 nanocubes wrapped by reduced graphene oxide as high-performance lithium-ion battery anodes
journal, January 2014

  • Kang, Wenpei; Tang, Yongbing; Li, Wenyue
  • Nanoscale, Vol. 6, Issue 12
  • DOI: 10.1039/C4NR00446A

Synergistic sodiation of cobalt oxide nanoparticles and conductive carbon nanotubes (CNTs) for sodium-ion batteries
journal, January 2016

  • Li, Qianqian; Wu, Jinsong; Xu, Junming
  • Journal of Materials Chemistry A, Vol. 4, Issue 22
  • DOI: 10.1039/C6TA02051H

Understanding materials challenges for rechargeable ion batteries with in situ transmission electron microscopy
journal, August 2017

  • Yuan, Yifei; Amine, Khalil; Lu, Jun
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms15806

Designing nanostructured Si anodes for high energy lithium ion batteries
journal, October 2012


Graphene Anchored with Co3O4 Nanoparticles as Anode of Lithium Ion Batteries with Enhanced Reversible Capacity and Cyclic Performance
journal, June 2010

  • Wu, Zhong-Shuai; Ren, Wencai; Wen, Lei
  • ACS Nano, Vol. 4, Issue 6, p. 3187-3194
  • DOI: 10.1021/nn100740x

The electrochemical behaviour of Co3O4 and CoO cathodes in high-temperature cells
journal, March 1982


(De)Lithiation Mechanism of Li/SeS x ( x = 0–7) Batteries Determined by in Situ Synchrotron X-ray Diffraction and X-ray Absorption Spectroscopy
journal, May 2013

  • Cui, Yanjie; Abouimrane, Ali; Lu, Jun
  • Journal of the American Chemical Society, Vol. 135, Issue 21
  • DOI: 10.1021/ja402597g

Oxidation energies of transition metal oxides within the GGA + U framework
journal, May 2006


Rationale for mixing exact exchange with density functional approximations
journal, December 1996

  • Perdew, John P.; Ernzerhof, Matthias; Burke, Kieron
  • The Journal of Chemical Physics, Vol. 105, Issue 22, p. 9982-9985
  • DOI: 10.1063/1.472933

Structural Changes in Silicon Anodes during Lithium Insertion/Extraction
journal, January 2004

  • Obrovac, M. N.; Christensen, Leif
  • Electrochemical and Solid-State Letters, Vol. 7, Issue 5
  • DOI: 10.1149/1.1652421

LixCoO2 (0<x<-1): A new cathode material for batteries of high energy density
journal, June 1980


The Electrochemical Reduction of Co[sub 3]O[sub 4] in a Lithium Cell
journal, January 2002

  • Larcher, D.; Sudant, G.; Leriche, J-B.
  • Journal of The Electrochemical Society, Vol. 149, Issue 3
  • DOI: 10.1149/1.1435358