Miscibility Gap Closure, Interface Morphology, and Phase Microstructure of 3D LixFePO 4 Nanoparticles from Surface Wetting and Coherency Strain

Welland, Michael J.; Karpeyev, Dmitry; O’Connor, Devin T.; Heinonen, Olle

doi:10.1021/acsnano.5b02555

Title: Miscibility Gap Closure, Interface Morphology, and Phase Microstructure of 3D Li_xFePO ₄ Nanoparticles from Surface Wetting and Coherency Strain

Journal Article · Thu Sep 10 00:00:00 EDT 2015 · ACS Nano

DOI:https://doi.org/10.1021/acsnano.5b02555· OSTI ID:1237941

Welland, Michael J. ^[1]; Karpeyev, Dmitry ^[2]; O’Connor, Devin T. ^[3]; Heinonen, Olle ^[4]

Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
Univ. of Chicago, IL (United States). Computation Inst.
Northwestern Univ., Evanston, IL (United States). McCormick School of Engineering
Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division; Univ. of Chicago, IL (United States). Computation Inst.

We study the mesoscopic effects which suppress phase-segregation in Li_xFePO₄ nanoparticles using a multiphysics phase-field model implement on a high performance cluster. We simulate 3D spherical particles of radii from 3nm to 40nm and examine the equilibrium microstructure and voltage profiles as a they depend on size and overall lithiation. The model includes anisotropic, concentration-dependent elastic moduli, misfit strain, and facet dependent surface wetting within a Cahn-Hilliard formulation. Here, we find that the miscibility gap vanishes for particles of radius ~ 5 nm, and the solubility limits change with overall particle lithiation. The corresponding voltage plateau, indicative of phase-segregation, changes in extent and also vanishes. Surface wetting is found to have a strong effect on stabilizing a variety of microstructures, exaggerating the shifting of solubility limits, and shortening the voltage plateau.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); US Department of Commerce

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1237941

Journal Information:: ACS Nano, Vol. 9, Issue 10; ISSN 1936-0851

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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References (50)

Properties and Promises of Nanosized Insertion Materials for Li-Ion Batteries Wagemaker, Marnix; Mulder, Fokko M. Accounts of Chemical Research, Vol. 46, Issue 5 https://doi.org/10.1021/ar2001793	journal	February 2012
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
Characterization of LiFePO4 as the cathode material for rechargeable lithium batteries Takahashi, Masaya; Tobishima, Shinichi; Takei, Koji Journal of Power Sources, Vol. 97-98 https://doi.org/10.1016/S0378-7753(01)00728-5	journal	July 2001
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
Phase Change in Li[sub x]FePO[sub 4] Yamada, Atsuo; Koizumi, Hiroshi; Sonoyama, Noriyuki Electrochemical and Solid-State Letters, Vol. 8, Issue 8 https://doi.org/10.1149/1.1945373	journal	January 2005
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
Size-Dependent Lithium Miscibility Gap in Nanoscale Li[sub 1−x]FePO[sub 4] Meethong, Nonglak; Huang, Hsiao-Ying Shadow; Carter, W. Craig Electrochemical and Solid-State Letters, Vol. 10, Issue 5 https://doi.org/10.1149/1.2710960	journal	January 2007
Room-temperature single-phase Li insertion/extraction in nanoscale LixFePO4 Gibot, Pierre; Casas-Cabanas, Montse; Laffont, Lydia Nature Materials, Vol. 7, Issue 9 https://doi.org/10.1038/nmat2245	journal	July 2008
Suppression of Phase Separation in LiFePO ₄ Nanoparticles During Battery Discharge Bai, Peng; Cogswell, Daniel A.; Bazant, Martin Z. Nano Letters, Vol. 11, Issue 11 https://doi.org/10.1021/nl202764f	journal	November 2011
Dynamic Solubility Limits in Nanosized Olivine LiFePO ₄ Wagemaker, Marnix; Singh, Deepak P.; Borghols, Wouter J. H. Journal of the American Chemical Society, Vol. 133, Issue 26 https://doi.org/10.1021/ja2026213	journal	July 2011
Isolation of Solid Solution Phases in Size-Controlled Li x FePO ₄ at Room Temperature Kobayashi, Genki; Nishimura, Shin-ichi; Park, Min-Sik Advanced Functional Materials, Vol. 19, Issue 3 https://doi.org/10.1002/adfm.200801522	journal	February 2009
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
Study of the Li-insertion/extraction process in LiFePO4/FePO4 Ramana, C. V.; Mauger, A.; Gendron, F. Journal of Power Sources, Vol. 187, Issue 2 https://doi.org/10.1016/j.jpowsour.2008.11.042	journal	February 2009
Study of the LiFePO ₄ /FePO ₄ Two-Phase System by High-Resolution Electron Energy Loss Spectroscopy Laffont, L.; Delacourt, C.; Gibot, P. Chemistry of Materials, Vol. 18, Issue 23 https://doi.org/10.1021/cm0617182	journal	November 2006
Electron Microscopy Study of the LiFePO[sub 4] to FePO[sub 4] Phase Transition Chen, Guoying; Song, Xiangyun; Richardson, Thomas J. Electrochemical and Solid-State Letters, Vol. 9, Issue 6 https://doi.org/10.1149/1.2192695	journal	January 2006
Size-Dependent Spinodal and Miscibility Gaps for Intercalation in Nanoparticles Burch, Damian; Bazant, Martin Z. Nano Letters, Vol. 9, Issue 11 https://doi.org/10.1021/nl9019787	journal	November 2009
Electrochemically Induced Phase Transformation in Nanoscale Olivines Li _{1− x} MPO ₄ (M = Fe, Mn) Meethong, Nonglak; Kao, Yu-Hua; Tang, Ming Chemistry of Materials, Vol. 20, Issue 19 https://doi.org/10.1021/cm801722f	journal	October 2008
Elastic properties of olivine ${Li}_{x} {FePO}_{4}$ from first principles Maxisch, Thomas; Ceder, Gerband Physical Review B, Vol. 73, Issue 17 https://doi.org/10.1103/PhysRevB.73.174112	journal	May 2006
The Role of Surface and Interface Energy on Phase Stability of Nanosized Insertion Compounds Wagemaker, Marnix; Mulder, Fokko M.; Van der Ven, Anton Advanced Materials, Vol. 21, Issue 25-26 https://doi.org/10.1002/adma.200803038	journal	April 2009
Anisotropic Phase Boundary Morphology in Nanoscale Olivine Electrode Particles Tang, Ming; Belak, James F.; Dorr, Milo R. The Journal of Physical Chemistry C, Vol. 115, Issue 11 https://doi.org/10.1021/jp109628m	journal	February 2011
Metastable Solid-Solution Phases in the LiFePO[sub 4]∕FePO[sub 4] System Chen, Guoying; Song, Xiangyun; Richardson, Thomas J. Journal of The Electrochemical Society, Vol. 154, Issue 7 https://doi.org/10.1149/1.2732189	journal	January 2007
Mesoscale Phase Distribution in Single Particles of LiFePO ₄ following Lithium Deintercalation Boesenberg, Ulrike; Meirer, Florian; Liu, Yijin Chemistry of Materials, Vol. 25, Issue 9 https://doi.org/10.1021/cm400106k	journal	April 2013
Spectroscopic studies of ${Li}_{x} Fe P O_{4}$ and ${Li}_{x} M_{0.03} {Fe}_{0.97} P O_{4}$ $(M = Cr, Cu, Al, Ti)$ Gouveia, D. X.; Lemos, V.; de Paiva, J. A. C. Physical Review B, Vol. 72, Issue 2 https://doi.org/10.1103/PhysRevB.72.024105	journal	July 2005
Effect of surface energies and nano-particle size distribution on open circuit voltage of Li-electrodes Van der Ven, A.; Wagemaker, M. Electrochemistry Communications, Vol. 11, Issue 4 https://doi.org/10.1016/j.elecom.2009.02.015	journal	April 2009
Surface effects on electrochemical properties of nano-sized LiFePO4 Julien, C. M.; Mauger, A.; Zaghib, K. Journal of Materials Chemistry, Vol. 21, Issue 27 https://doi.org/10.1039/c0jm04190d	journal	January 2011
Relationship between local structure and electrochemical performance of LiFePO4 in Li-ion batteries Zaghib, K.; Mauger, A.; Gendron, F. Ionics, Vol. 14, Issue 4 https://doi.org/10.1007/s11581-007-0181-0	journal	December 2007
IR Near-Field Spectroscopy and Imaging of Single Li _x FePO ₄ Microcrystals Lucas, I. T.; McLeod, A. S.; Syzdek, J. S. Nano Letters, Vol. 15, Issue 1 https://doi.org/10.1021/nl5010898	journal	December 2014
First-principles study of surface properties of $Li Fe P O_{4}$ : Surface energy, structure, Wulff shape, and surface redox potential Wang, L.; Zhou, F.; Meng, Y. S. Physical Review B, Vol. 76, Issue 16 https://doi.org/10.1103/PhysRevB.76.165435	journal	October 2007
Theory of Coherent Nucleation in Phase-Separating Nanoparticles Cogswell, Daniel A.; Bazant, Martin Z. Nano Letters, Vol. 13, Issue 7 https://doi.org/10.1021/nl400497t	journal	May 2013
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
Phase Separation Dynamics in Isotropic Ion-Intercalation Particles Zeng, Yi; Bazant, Martin Z. SIAM Journal on Applied Mathematics, Vol. 74, Issue 4 https://doi.org/10.1137/130937548	journal	January 2014
The persistence of phase-separation in LiFePO4 with two-dimensional Li+ transport: The Cahn–Hilliard-reaction equation and the role of defects Dargaville, S.; Farrell, T. W. Electrochimica Acta, Vol. 94 https://doi.org/10.1016/j.electacta.2013.01.082	journal	April 2013
Finite element model of ionic nanowires with size-dependent mechanical properties determined by ab initio calculations Yvonnet, J.; Mitrushchenkov, A.; Chambaud, G. Computer Methods in Applied Mechanics and Engineering, Vol. 200, Issue 5-8 https://doi.org/10.1016/j.cma.2010.09.007	journal	January 2011
Phase Field Theory of Heterogeneous Crystal Nucleation Gránásy, László; Pusztai, Tamás; Saylor, David Physical Review Letters, Vol. 98, Issue 3 https://doi.org/10.1103/PhysRevLett.98.035703	journal	January 2007
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
Critical point wetting Cahn, John W. The Journal of Chemical Physics, Vol. 66, Issue 8 https://doi.org/10.1063/1.434402	journal	April 1977
Elastically constrained phase-separation dynamics competing with the charge process in the LiFePO4/FePO4 system Ichitsubo, Tetsu; Tokuda, Kazuya; Yagi, Shunsuke Journal of Materials Chemistry A, Vol. 1, Issue 7 https://doi.org/10.1039/c2ta01102f	journal	January 2013
The thermodynamic origin of hysteresis in insertion batteries Dreyer, Wolfgang; Jamnik, Janko; Guhlke, Clemens Nature Materials, Vol. 9, Issue 5 https://doi.org/10.1038/nmat2730	journal	April 2010
Phase Transformation Dynamics in Porous Battery Electrodes Ferguson, Todd R.; Bazant, Martin Z. Electrochimica Acta, Vol. 146 https://doi.org/10.1016/j.electacta.2014.08.083	journal	November 2014
Configurational Electronic Entropy and the Phase Diagram of Mixed-Valence Oxides: The Case of ${Li}_{x} {FePO}_{4}$ Zhou, Fei; Maxisch, Thomas; Ceder, Gerbrand Physical Review Letters, Vol. 97, Issue 15 https://doi.org/10.1103/PhysRevLett.97.155704	journal	October 2006
Kinetics of non-equilibrium lithium incorporation in LiFePO4 Malik, Rahul; Zhou, Fei; Ceder, G. Nature Materials, Vol. 10, Issue 8 https://doi.org/10.1038/nmat3065	journal	July 2011
Model for the Particle Size, Overpotential, and Strain Dependence of Phase Transition Pathways in Storage Electrodes: Application to Nanoscale Olivines Tang, M.; Huang, H. -Y.; Meethong, N. Chemistry of Materials, Vol. 21, Issue 8 https://doi.org/10.1021/cm803172s	journal	April 2009
A method for calculating surface stress and surface elastic constants by molecular dynamics: application to the surface of crystal and amorphous silicon Izumi, S.; Hara, S.; Kumagai, T. Thin Solid Films, Vol. 467, Issue 1-2 https://doi.org/10.1016/j.tsf.2004.03.034	journal	November 2004
Composition, structure, and stability of ${RuO}_{2} (110)$ as a function of oxygen pressure Reuter, Karsten; Scheffler, Matthias Physical Review B, Vol. 65, Issue 3 https://doi.org/10.1103/PhysRevB.65.035406	journal	December 2001
Size-dependent elastic properties of nanosized structural elements Miller, Ronald E.; Shenoy, Vijay B. Nanotechnology, Vol. 11, Issue 3 https://doi.org/10.1088/0957-4484/11/3/301	journal	July 2000
Efficient Management of Parallelism in Object-Oriented Numerical Software Libraries Balay, Satish; Gropp, William D.; McInnes, Lois Curfman Modern Software Tools for Scientific Computing https://doi.org/10.1007/978-1-4612-1986-6_8	book	January 1997
Automated Solution of Differential Equations by the Finite Element Method Logg, Anders; Mardal, Kent-Andre; Wells, Garth Lecture Notes in Computational Science and Engineering https://doi.org/10.1007/978-3-642-23099-8	book	January 2012
A compiler for variational forms Kirby, Robert C.; Logg, Anders ACM Transactions on Mathematical Software, Vol. 32, Issue 3 https://doi.org/10.1145/1163641.1163644	journal	September 2006
Gmsh: A 3-D finite element mesh generator with built-in pre- and post-processing facilities Geuzaine, Christophe; Remacle, Jean-François International Journal for Numerical Methods in Engineering, Vol. 79, Issue 11 https://doi.org/10.1002/nme.2579	journal	September 2009

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Title: Miscibility Gap Closure, Interface Morphology, and Phase Microstructure of 3D LixFePO 4 Nanoparticles from Surface Wetting and Coherency Strain

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Title: Miscibility Gap Closure, Interface Morphology, and Phase Microstructure of 3D Li_xFePO ₄ Nanoparticles from Surface Wetting and Coherency Strain