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

Title: Topological defect dynamics in operando battery nanoparticles

Abstract

Topological defects can markedly alter nanomaterial properties. This presents opportunities for "defect engineering," where desired functionalities are generated through defect manipulation. However, imaging defects in working devices with nanoscale resolution remains elusive. We report three-dimensional imaging of dislocation dynamics in individual battery cathode nanoparticles under operando conditions using Bragg coherent diffractive imaging. Dislocations are static at room temperature and mobile during charge transport. During the structural phase transformation, the lithium-rich phase nucleates near the dislocation and spreads inhomogeneously. The dislocation field is a local probe of elastic properties, and we find that a region of the material exhibits a negative Poisson's ratio at high voltage. Operando dislocation imaging thus opens a powerful avenue for facilitating improvement and rational design of nanostructured materials.

Authors:
; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1391962
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Science
Additional Journal Information:
Journal Volume: 348; Journal Issue: 6241; Journal ID: ISSN 0036-8075
Publisher:
AAAS
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY; 25 ENERGY STORAGE

Citation Formats

Ulvestad, A., Singer, A., Clark, J. N., Cho, H. M., Kim, J. W., Harder, R., Maser, J., Meng, Y. S., and Shpyrko, O. G. Topological defect dynamics in operando battery nanoparticles. United States: N. p., 2015. Web. doi:10.1126/science.aaa1313.
Ulvestad, A., Singer, A., Clark, J. N., Cho, H. M., Kim, J. W., Harder, R., Maser, J., Meng, Y. S., & Shpyrko, O. G. Topological defect dynamics in operando battery nanoparticles. United States. doi:10.1126/science.aaa1313.
Ulvestad, A., Singer, A., Clark, J. N., Cho, H. M., Kim, J. W., Harder, R., Maser, J., Meng, Y. S., and Shpyrko, O. G. Thu . "Topological defect dynamics in operando battery nanoparticles". United States. doi:10.1126/science.aaa1313.
@article{osti_1391962,
title = {Topological defect dynamics in operando battery nanoparticles},
author = {Ulvestad, A. and Singer, A. and Clark, J. N. and Cho, H. M. and Kim, J. W. and Harder, R. and Maser, J. and Meng, Y. S. and Shpyrko, O. G.},
abstractNote = {Topological defects can markedly alter nanomaterial properties. This presents opportunities for "defect engineering," where desired functionalities are generated through defect manipulation. However, imaging defects in working devices with nanoscale resolution remains elusive. We report three-dimensional imaging of dislocation dynamics in individual battery cathode nanoparticles under operando conditions using Bragg coherent diffractive imaging. Dislocations are static at room temperature and mobile during charge transport. During the structural phase transformation, the lithium-rich phase nucleates near the dislocation and spreads inhomogeneously. The dislocation field is a local probe of elastic properties, and we find that a region of the material exhibits a negative Poisson's ratio at high voltage. Operando dislocation imaging thus opens a powerful avenue for facilitating improvement and rational design of nanostructured materials.},
doi = {10.1126/science.aaa1313},
journal = {Science},
issn = {0036-8075},
number = 6241,
volume = 348,
place = {United States},
year = {2015},
month = {6}
}

Works referenced in this record:

Bragg x-ray ptychography of a silicon crystal: Visualization of the dislocation strain field and the production of a vortex beam
journal, March 2013


Molecular Dynamics Simulations of SOC-Dependent Elasticity of Li x Mn 2 O 4 Spinels in Li-Ion Batteries
journal, January 2013

  • Lee, Seungjun; Park, Jonghyun; Sastry, Ann Marie
  • Journal of The Electrochemical Society, Vol. 160, Issue 6
  • DOI: 10.1149/2.147306jes

Poisson's ratio and modern materials
journal, October 2011

  • Greaves, G. N.; Greer, A. L.; Lakes, R. S.
  • Nature Materials, Vol. 10, Issue 11
  • DOI: 10.1038/nmat3134

Lithium Batteries and Cathode Materials
journal, October 2004

  • Whittingham, M. Stanley
  • Chemical Reviews, Vol. 104, Issue 10, p. 4271-4302
  • DOI: 10.1021/cr020731c

Issues and challenges facing rechargeable lithium batteries
journal, November 2001

  • Tarascon, J.-M.; Armand, M.
  • Nature, Vol. 414, Issue 6861, p. 359-367
  • DOI: 10.1038/35104644

Synchrotron x-ray reticulography: principles and applications
journal, January 1999


Three-Dimensional Imaging of Microstructure in Au Nanocrystals
journal, April 2003


Nucleation on dislocations
journal, November 1970


A study of room-temperature LixMn1.5Ni0.5O4 solid solutions
journal, January 2015

  • Saravanan, Kuppan; Jarry, Angelique; Kostecki, Robert
  • Scientific Reports, Vol. 5, Issue 1
  • DOI: 10.1038/srep08027

Measurement of the displacement field of dislocations to 0.03 Å by electron microscopy
journal, May 2003

  • Hÿtch, Martin J.; Putaux, Jean-Luc; Pénisson, Jean-Michel
  • Nature, Vol. 423, Issue 6937
  • DOI: 10.1038/nature01638

Numerical Simulation of Intercalation-Induced Stress in Li-Ion Battery Electrode Particles
journal, January 2007

  • Zhang, Xiangchun; Shyy, Wei; Marie Sastry, Ann
  • Journal of The Electrochemical Society, Vol. 154, Issue 10
  • DOI: 10.1149/1.2759840

High-resolution three-dimensional partially coherent diffraction imaging
journal, January 2012

  • Clark, J. N.; Huang, X.; Harder, R.
  • Nature Communications, Vol. 3, Issue 1
  • DOI: 10.1038/ncomms1994

Rational Defect Introduction in Silicon Nanowires
journal, April 2013

  • Shin, Naechul; Chi, Miaofang; Howe, Jane Y.
  • Nano Letters, Vol. 13, Issue 5, p. 1928-1933
  • DOI: 10.1021/nl3042728

Phase transformations and volume changes in spinel LixMn2O4
journal, November 2000


Direct Observation of Individual Dislocations by X‐Ray Diffraction
journal, March 1958


Coherent diffraction imaging of nanoscale strain evolution in a single crystal under high pressure
journal, April 2013

  • Yang, Wenge; Huang, Xiaojing; Harder, Ross
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms2661

Nanoconfinement effects in energy storage materials
journal, January 2011

  • Fichtner, Maximilian
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 48
  • DOI: 10.1039/c1cp22547b

Capturing metastable structures during high-rate cycling of LiFePO4 nanoparticle electrodes
journal, June 2014


Single Particle Nanomechanics in Operando Batteries via Lensless Strain Mapping
journal, August 2014

  • Ulvestad, Andrew; Singer, Andrej; Cho, Hyung-Man
  • Nano Letters, Vol. 14, Issue 9
  • DOI: 10.1021/nl501858u

Ultrafast Three-Dimensional Imaging of Lattice Dynamics in Individual Gold Nanocrystals
journal, May 2013


Nonequilibrium Structural Dynamics of Nanoparticles in LiNi 1/2 Mn 3/2 O 4 Cathode under Operando Conditions
journal, August 2014

  • Singer, Andrej; Ulvestad, Andrew; Cho, Hyung-Man
  • Nano Letters, Vol. 14, Issue 9
  • DOI: 10.1021/nl502332b

Longitudinal coherence function in X-ray imaging of crystals
journal, January 2009

  • Leake, Steven J.; Newton, Marcus C.; Harder, Ross
  • Optics Express, Vol. 17, Issue 18
  • DOI: 10.1364/OE.17.015853

Factors affecting Li mobility in spinel LiMn2O4—A first-principles study by GGA and GGA+U methods
journal, August 2010


Comparative Study of LiNi 0.5 Mn 1.5 O 4 - δ and LiNi 0.5 Mn 1.5 O 4 Cathodes Having Two Crystallographic Structures:  Fdm and P 4 3 32
journal, March 2004

  • Kim, J. -H.; Myung, S. -T.; Yoon, C. S.
  • Chemistry of Materials, Vol. 16, Issue 5
  • DOI: 10.1021/cm035050s

Charge Density Wave Dislocation as Revealed by Coherent X-Ray Diffraction
journal, September 2005


Dislocation Based Stress Developments in Lithium-Ion Batteries
journal, January 2012

  • Shadow Huang, Hsiao-Ying; Wang, Yi-Xu
  • Journal of The Electrochemical Society, Vol. 159, Issue 6
  • DOI: 10.1149/2.090206jes

A Mathematical Model of Stress Generation and Fracture in Lithium Manganese Oxide
journal, January 2006

  • Christensen, John; Newman, John
  • Journal of The Electrochemical Society, Vol. 153, Issue 6
  • DOI: 10.1149/1.2185287

Electronic, Structural, and Electrochemical Properties of LiNi x Cu y Mn 2– xy O 4 (0 < x < 0.5, 0 < y < 0.5) High-Voltage Spinel Materials
journal, June 2011

  • Yang, Ming-Che; Xu, Bo; Cheng, Ju-Hsiang
  • Chemistry of Materials, Vol. 23, Issue 11
  • DOI: 10.1021/cm200042z

Method for the Detection of Dislocations in Silicon by X-Ray Extinction Contrast
journal, June 1958


TEM Study of Electrochemical Cycling-Induced Damage and Disorder in LiCoO[sub 2] Cathodes for Rechargeable Lithium Batteries
journal, January 1999

  • Wang, Haifeng
  • Journal of The Electrochemical Society, Vol. 146, Issue 2
  • DOI: 10.1149/1.1391631

Effect of Ni/Mn Ordering on Elementary Polarizations of LiNi 0.5 Mn 1.5 O 4 Spinel and Its Nanostructured Electrode
journal, January 2013

  • Cho, Hyung-Man; Meng, Ying Shirley
  • Journal of The Electrochemical Society, Vol. 160, Issue 9
  • DOI: 10.1149/2.059309jes

Molecular Auxetic Behavior of Epitaxial Co-Ferrite Spinel Thin Film
journal, February 2010

  • Valant, Matjaz; Axelsson, Anna-Karin; Aguesse, Frederic
  • Advanced Functional Materials, Vol. 20, Issue 4
  • DOI: 10.1002/adfm.200901762

Graphene gets designer defects
journal, May 2010


Nanoscale strain mapping in battery nanostructures
journal, February 2014

  • Ulvestad, A.; Cho, H. M.; Harder, R.
  • Applied Physics Letters, Vol. 104, Issue 7
  • DOI: 10.1063/1.4866030