Operando real-space imaging of a structural phase transformation in the high-voltage electrode LixNi0.5Mn1.5O4

Sun, Yifei; Hy, Sunny; Hua, Nelson; Wingert, James; Harder, Ross; Meng, Ying Shirley; Shpyrko, Oleg; Singer, Andrej

doi:10.1038/s41467-024-55010-6

Operando real-space imaging of a structural phase transformation in the high-voltage electrode LixNi0.5Mn1.5O4

Journal Article · Sun Dec 29 23:00:00 EST 2024 · Nature Communications

DOI:https://doi.org/10.1038/s41467-024-55010-6· OSTI ID:2484094

; Hy, Sunny; Hua, Nelson; Wingert, James; Harder, Ross; ; Shpyrko, Oleg;

Abstract

Discontinuous solid-solid phase transformations play a pivotal role in determining the properties of rechargeable battery electrodes. By leveraging operando Bragg Coherent Diffractive Imaging (BCDI), we investigate the discontinuous phase transformation in Li _x Ni _0.5 Mn _1.5 O ₄ within an operational Li metal coin cell. Throughout Li-intercalation, we directly observe the nucleation and growth of the Li-rich phase within the initially charged Li-poor phase in a 500 nm particle. Supported by the microelasticity model, the operando imaging unveils an evolution from a curved coherent to a planar semi-coherent interface driven by dislocation dynamics. Our data indicates negligible kinetic limitations from interface propagation impacting the transformation kinetics, even at a discharge rate of C/2 (80 mA/g). This study highlights BCDI’s capability to decode complex operando diffraction data, offering exciting opportunities to study nanoscale phase transformations with various stimuli.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0001805; AC02-06CH11357

OSTI ID:: 2484094

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 15; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United Kingdom

Language:: English

References (38)

Kinetics of Materials Balluffi, Robert W.; Allen, Samuel M.; Carter, W. Craig https://doi.org/10.1002/0471749311	book	September 2005
Structural Phase Transformations in Nanoscale Systems Wilde, Gerhard Advanced Engineering Materials, Vol. 23, Issue 5 https://doi.org/10.1002/adem.202001387	journal	February 2021
A Kinetic Two-Phase and Equilibrium Solid Solution in Spinel Li4+xTi5O12 Wagemaker, M.; Simon, D. R.; Kelder, E. M. Advanced Materials, Vol. 18, Issue 23 https://doi.org/10.1002/adma.200601636	journal	December 2006
Defects, Entropy, and the Stabilization of Alternative Phase Boundary Orientations in Battery Electrode Particles Heo, Tae Wook; Tang, Ming; Chen, Long-Qing Advanced Energy Materials, Vol. 6, Issue 6 https://doi.org/10.1002/aenm.201501759	journal	January 2016
The Fine Line between a Two-Phase and Solid-Solution Phase Transformation and Highly Mobile Phase Interfaces in Spinel Li ₄₊ _x Ti ₅ O ₁₂ Ganapathy, Swapna; Vasileiadis, Alexandros; Heringa, Jouke R. Advanced Energy Materials, Vol. 7, Issue 9 https://doi.org/10.1002/aenm.201601781	journal	December 2016
Disorder Dynamics in Battery Nanoparticles During Phase Transitions Revealed by Operando Single‐Particle Diffraction Huang, Jason J.; Weinstock, Daniel; Hirsh, Hayley Advanced Energy Materials, Vol. 12, Issue 12 https://doi.org/10.1002/aenm.202103521	journal	February 2022
Cobalt‐Free Cathode Materials: Families and their Prospects Zhao, Hong; Lam, Wai‐Yu Ashley; Sheng, Li Advanced Energy Materials, Vol. 12, Issue 16 https://doi.org/10.1002/aenm.202103894	journal	February 2022
Lithium extraction/insertion in LiFePO4: an X-ray diffraction and Mössbauer spectroscopy study Andersson, A. Solid State Ionics, Vol. 130, Issue 1-2 https://doi.org/10.1016/S0167-2738(00)00311-8	journal	May 2000
Predicting equilibrium shape of precipitates as function of coherency state Shi, R.; Ma, N.; Wang, Y. Acta Materialia, Vol. 60, Issue 10 https://doi.org/10.1016/j.actamat.2012.04.019	journal	June 2012
Intercalation dynamics in rechargeable battery materials: General theory and phase-transformation waves in LiFePO4 Singh, Gogi K.; Ceder, Gerbrand; Bazant, Martin Z. Electrochimica Acta, Vol. 53, Issue 26 https://doi.org/10.1016/j.electacta.2008.03.083	journal	November 2008
Synchrotron X-ray Analytical Techniques for Studying Materials Electrochemistry in Rechargeable Batteries Lin, Feng; Liu, Yijin; Yu, Xiqian Chemical Reviews, Vol. 117, Issue 21 https://doi.org/10.1021/acs.chemrev.7b00007	journal	September 2017
X-ray Nanoimaging of Crystal Defects in Single Grains of Solid-State Electrolyte Li _{7–3 x} Al _x La ₃ Zr ₂ O ₁₂ Sun, Yifei; Gorobstov, Oleg; Mu, Linqin Nano Letters, Vol. 21, Issue 11 https://doi.org/10.1021/acs.nanolett.1c00315	journal	April 2021
Effect of Surface Modification on Nano-Structured LiNi _0.5 Mn _1.5 O ₄ Spinel Materials Cho, Hyung-Man; Chen, Michael Vincent; MacRae, Alex C. ACS Applied Materials & Interfaces, Vol. 7, Issue 30 https://doi.org/10.1021/acsami.5b01392	journal	July 2015
Understanding Li Diffusion in Li-Intercalation Compounds Van der Ven, Anton; Bhattacharya, Jishnu; Belak, Anna A. Accounts of Chemical Research, Vol. 46, Issue 5 https://doi.org/10.1021/ar200329r	journal	May 2012
Theory of Chemical Kinetics and Charge Transfer based on Nonequilibrium Thermodynamics Bazant, Martin Z. Accounts of Chemical Research, Vol. 46, Issue 5 https://doi.org/10.1021/ar300145c	journal	June 2012
Direct Evidence of Concurrent Solid-Solution and Two-Phase Reactions and the Nonequilibrium Structural Evolution of LiFePO ₄ Sharma, Neeraj; Guo, Xianwei; Du, Guodong Journal of the American Chemical Society, Vol. 134, Issue 18 https://doi.org/10.1021/ja301187u	journal	April 2012
Single Particle Nanomechanics in Operando Batteries via Lensless Strain Mapping Ulvestad, Andrew; Singer, Andrej; Cho, Hyung-Man Nano Letters, Vol. 14, Issue 9 https://doi.org/10.1021/nl501858u	journal	August 2014
Nonequilibrium Structural Dynamics of Nanoparticles in LiNi _1/2 Mn _3/2 O ₄ Cathode under Operando Conditions Singer, Andrej; Ulvestad, Andrew; Cho, Hyung-Man Nano Letters, Vol. 14, Issue 9 https://doi.org/10.1021/nl502332b	journal	August 2014
Coherency Strain and the Kinetics of Phase Separation in LiFePO ₄ Nanoparticles Cogswell, Daniel A.; Bazant, Martin Z. ACS Nano, Vol. 6, Issue 3 https://doi.org/10.1021/nn204177u	journal	February 2012
Three-dimensional mapping of a deformation field inside a nanocrystal Pfeifer, Mark A.; Williams, Garth J.; Vartanyants, Ivan A. Nature, Vol. 442, Issue 7098 https://doi.org/10.1038/nature04867	journal	July 2006
Phase transformation mechanism in lithium manganese nickel oxide revealed by single-crystal hard X-ray microscopy Kuppan, Saravanan; Xu, Yahong; Liu, Yijin Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms14309	journal	February 2017
Lithium deintercalation in LiFePO4 nanoparticles via a domino-cascade model Delmas, C.; Maccario, M.; Croguennec, L. Nature Materials, Vol. 7, Issue 8 https://doi.org/10.1038/nmat2230	journal	July 2008
Coherent X-ray diffraction imaging of strain at the nanoscale Robinson, Ian; Harder, Ross Nature Materials, Vol. 8, Issue 4 https://doi.org/10.1038/nmat2400	journal	April 2009
Three-dimensional imaging of dislocation propagation during crystal growth and dissolution Clark, Jesse N.; Ihli, Johannes; Schenk, Anna S. Nature Materials, Vol. 14, Issue 8 https://doi.org/10.1038/nmat4320	journal	June 2015
Nucleation of dislocations and their dynamics in layered oxide cathode materials during battery charging Singer, A.; Zhang, M.; Hy, S. Nature Energy, Vol. 3, Issue 8 https://doi.org/10.1038/s41560-018-0184-2	journal	July 2018
Developing high-voltage spinel LiNi _0.5 Mn _1.5 O ₄ cathodes for high-energy-density lithium-ion batteries: current achievements and future prospects Liang, Gemeng; Peterson, Vanessa K.; See, Khay Wai Journal of Materials Chemistry A, Vol. 8, Issue 31 https://doi.org/10.1039/D0TA02812F	journal	January 2020
ESRF-EBS: The Extremely Brilliant Source Project Raimondi, Pantaleo Synchrotron Radiation News, Vol. 29, Issue 6 https://doi.org/10.1080/08940886.2016.1244462	journal	November 2016
An algorithm for Bragg coherent x-ray diffractive imaging of highly strained nanocrystals Wang, Ziyi; Gorobtsov, Oleg; Singer, Andrej New Journal of Physics, Vol. 22, Issue 1 https://doi.org/10.1088/1367-2630/ab61db	journal	January 2020
Three-Dimensional Imaging of Microstructure in Au Nanocrystals Williams, G. J.; Pfeifer, M. A.; Vartanyants, I. A. Physical Review Letters, Vol. 90, Issue 17 https://doi.org/10.1103/PhysRevLett.90.175501	journal	April 2003
Evolution of ferroelastic domain walls during phase transitions in barium titanate nanoparticles Diao, Jiecheng; Shi, Xiaowen; Assefa, Tadesse A. Physical Review Materials, Vol. 4, Issue 10 https://doi.org/10.1103/PhysRevMaterials.4.106001	journal	October 2020
Capturing metastable structures during high-rate cycling of LiFePO4 nanoparticle electrodes Liu, H.; Strobridge, F. C.; Borkiewicz, O. J. Science, Vol. 344, Issue 6191 https://doi.org/10.1126/science.1252817	journal	June 2014
Topological defect dynamics in operando battery nanoparticles Ulvestad, A.; Singer, A.; Clark, J. N. Science, Vol. 348, Issue 6241 https://doi.org/10.1126/science.aaa1313	journal	June 2015
Phase Transitions in Li[sub 1−δ]Ni[sub 0.5]Mn[sub 1.5]O[sub 4] during Cycling at 5 V Kim, J. -H.; Yoon, C. S.; Myung, S. -T. Electrochemical and Solid-State Letters, Vol. 7, Issue 7 https://doi.org/10.1149/1.1753252	journal	January 2004
Discharge Model for the Lithium Iron-Phosphate Electrode Srinivasan, Venkat; Newman, John Journal of The Electrochemical Society, Vol. 151, Issue 10 https://doi.org/10.1149/1.1785012	journal	January 2004
Phospho-olivines as Positive-Electrode Materials for Rechargeable Lithium Batteries Padhi, A. K. Journal of The Electrochemical Society, Vol. 144, Issue 4, p. 1188-1194 https://doi.org/10.1149/1.1837571	journal	April 1997
Will Sodium Layered Oxides Ever Be Competitive for Sodium Ion Battery Applications? Mariyappan, Sathiya; Wang, Qing; Tarascon, Jean Marie Journal of The Electrochemical Society, Vol. 165, Issue 16 https://doi.org/10.1149/2.0201816jes	journal	January 2018
Effect of Ni/Mn Ordering on Elementary Polarizations of LiNi _0.5 Mn _1.5 O ₄ Spinel and Its Nanostructured Electrode Cho, Hyung-Man; Meng, Ying Shirley Journal of The Electrochemical Society, Vol. 160, Issue 9 https://doi.org/10.1149/2.059309jes	journal	January 2013
Phase Transformations in Metals and Alloys (Revised Reprint) Porter, David A.; Easterling, Kenneth E.; Easterling, Kenneth E. https://doi.org/10.1201/9781439883570	book	February 2009

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