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

Abstract

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.

Authors:

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.

Publication Date:: Thu Sep 10 00:00:00 EDT 2015

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

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

OSTI Identifier:: 1237941

Grant/Contract Number:: AC02-06CH11357

Resource Type:: Accepted Manuscript

Journal Name:: ACS Nano

Additional Journal Information:: Journal Volume: 9; Journal Issue: 10; Journal ID: ISSN 1936-0851

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE; 77 NANOSCIENCE AND NANOTECHNOLOGY; Li-ion battery; LiFePO4; coherency strain; interface morphology; nanoparticles; phase-field model; surface wetting

Citation Formats


                    Welland, Michael J., Karpeyev, Dmitry, O’Connor, Devin T., and Heinonen, Olle. Miscibility Gap Closure, Interface Morphology, and Phase Microstructure of 3D LixFePO 4 Nanoparticles from Surface Wetting and Coherency Strain.  United States: N. p., 2015. 
Web.  doi:10.1021/acsnano.5b02555.

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                    Welland, Michael J., Karpeyev, Dmitry, O’Connor, Devin T., & Heinonen, Olle. Miscibility Gap Closure, Interface Morphology, and Phase Microstructure of 3D LixFePO 4 Nanoparticles from Surface Wetting and Coherency Strain.  United States.  https://doi.org/10.1021/acsnano.5b02555

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                    Welland, Michael J., Karpeyev, Dmitry, O’Connor, Devin T., and Heinonen, Olle. Thu .  
"Miscibility Gap Closure, Interface Morphology, and Phase Microstructure of 3D LixFePO 4 Nanoparticles from Surface Wetting and Coherency Strain".  United States.  https://doi.org/10.1021/acsnano.5b02555.  https://www.osti.gov/servlets/purl/1237941.

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@article{osti_1237941,

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

  author       = {Welland, Michael J. and Karpeyev, Dmitry and O’Connor, Devin T. and Heinonen, Olle},

  abstractNote = {We study the mesoscopic effects which suppress phase-segregation in LixFePO4 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.},

  doi          = {10.1021/acsnano.5b02555},

  journal      = {ACS Nano},

  number       = 10,

  volume       = 9,

  place        = {United States},

  year         = {Thu Sep 10 00:00:00 EDT 2015},

  month        = {Thu Sep 10 00:00:00 EDT 2015}

}

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

Abstract

Citation Formats

Properties and Promises of Nanosized Insertion Materials for Li-Ion Batteries journal, February 2012

Understanding Li Diffusion in Li-Intercalation Compounds journal, May 2012

Characterization of LiFePO4 as the cathode material for rechargeable lithium batteries journal, July 2001

Lithium deintercalation in LiFePO4 nanoparticles via a domino-cascade model journal, July 2008

Phase Change in Li[sub x]FePO[sub 4] journal, January 2005

Discharge Model for the Lithium Iron-Phosphate Electrode journal, January 2004

Phospho-olivines as Positive-Electrode Materials for Rechargeable Lithium Batteries journal, April 1997

Size-Dependent Lithium Miscibility Gap in Nanoscale Li[sub 1−x]FePO[sub 4] journal, January 2007

Room-temperature single-phase Li insertion/extraction in nanoscale LixFePO4 journal, July 2008

Suppression of Phase Separation in LiFePO 4 Nanoparticles During Battery Discharge journal, November 2011

Dynamic Solubility Limits in Nanosized Olivine LiFePO 4 journal, July 2011

Isolation of Solid Solution Phases in Size-Controlled Li x FePO 4 at Room Temperature journal, February 2009

Coherency Strain and the Kinetics of Phase Separation in LiFePO 4 Nanoparticles journal, February 2012

Study of the Li-insertion/extraction process in LiFePO4/FePO4 journal, February 2009

Study of the LiFePO 4 /FePO 4 Two-Phase System by High-Resolution Electron Energy Loss Spectroscopy journal, November 2006

Electron Microscopy Study of the LiFePO[sub 4] to FePO[sub 4] Phase Transition journal, January 2006

Size-Dependent Spinodal and Miscibility Gaps for Intercalation in Nanoparticles journal, November 2009

Electrochemically Induced Phase Transformation in Nanoscale Olivines Li 1− x MPO 4 (M = Fe, Mn) journal, October 2008

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The Role of Surface and Interface Energy on Phase Stability of Nanosized Insertion Compounds journal, April 2009

Anisotropic Phase Boundary Morphology in Nanoscale Olivine Electrode Particles journal, February 2011

Metastable Solid-Solution Phases in the LiFePO[sub 4]∕FePO[sub 4] System journal, January 2007

Mesoscale Phase Distribution in Single Particles of LiFePO 4 following Lithium Deintercalation 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 ) journal, July 2005

Effect of surface energies and nano-particle size distribution on open circuit voltage of Li-electrodes journal, April 2009

Surface effects on electrochemical properties of nano-sized LiFePO4 journal, January 2011

Relationship between local structure and electrochemical performance of LiFePO4 in Li-ion batteries journal, December 2007

IR Near-Field Spectroscopy and Imaging of Single Li x FePO 4 Microcrystals journal, December 2014

First-principles study of surface properties of Li Fe P O 4 : Surface energy, structure, Wulff shape, and surface redox potential journal, October 2007

Theory of Coherent Nucleation in Phase-Separating Nanoparticles journal, May 2013

Intercalation dynamics in rechargeable battery materials: General theory and phase-transformation waves in LiFePO4 journal, November 2008

Phase Separation Dynamics in Isotropic Ion-Intercalation Particles 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 journal, April 2013

Finite element model of ionic nanowires with size-dependent mechanical properties determined by ab initio calculations journal, January 2011

Phase Field Theory of Heterogeneous Crystal Nucleation journal, January 2007

Theory of Chemical Kinetics and Charge Transfer based on Nonequilibrium Thermodynamics journal, June 2012

Critical point wetting journal, April 1977

Elastically constrained phase-separation dynamics competing with the charge process in the LiFePO4/FePO4 system journal, January 2013

The thermodynamic origin of hysteresis in insertion batteries journal, April 2010

Phase Transformation Dynamics in Porous Battery Electrodes journal, November 2014

Configurational Electronic Entropy and the Phase Diagram of Mixed-Valence Oxides: The Case of Li x FePO 4 journal, October 2006

Kinetics of non-equilibrium lithium incorporation in LiFePO4 journal, July 2011

Model for the Particle Size, Overpotential, and Strain Dependence of Phase Transition Pathways in Storage Electrodes: Application to Nanoscale Olivines 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 journal, November 2004

Composition, structure, and stability of RuO 2 ( 110 ) as a function of oxygen pressure journal, December 2001

Size-dependent elastic properties of nanosized structural elements journal, July 2000

Efficient Management of Parallelism in Object-Oriented Numerical Software Libraries book, January 1997

Automated Solution of Differential Equations by the Finite Element Method book, January 2012

A compiler for variational forms journal, September 2006

Gmsh: A 3-D finite element mesh generator with built-in pre- and post-processing facilities journal, September 2009

A phase-field study of the effect of local deformation velocity on lithiation-induced stress in wire-like structures journal, February 2019

Phase Field Modeling of Coupled Phase Separation and Diffusion-Induced Stress in Lithium Iron Phosphate Particles Reconstructed From Synchrotron Nano X-ray Tomography journal, April 2019

Three-dimensional localization of nanoscale battery reactions using soft X-ray tomography journal, March 2018

Multiphase Porous Electrode Theory journal, January 2017

Toward Optimal Performance and In-Depth Understanding of Spinel Li 4 Ti 5 O 12 Electrodes through Phase Field Modeling journal, February 2018

Phase-field study of surface irregularities of a cathode particle during intercalation journal, August 2018

An Extended Formulation of Butler-Volmer Electrochemical Reaction Kinetics Including the Influence of Mechanics journal, January 2019

Phase transformation and fracture in single Li x FePO 4 cathode particles: a phase-field approach to Li–ion intercalation and fracture journal, March 2016

Three-dimensional localization of nanoscale battery reactions using soft X-ray tomography. text, January 2018

Three-dimensional localization of nanoscale battery reactions using soft X-ray tomography. text, January 2018

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

Properties and Promises of Nanosized Insertion Materials for Li-Ion Batteries
journal, February 2012

Understanding Li Diffusion in Li-Intercalation Compounds
journal, May 2012

Characterization of LiFePO4 as the cathode material for rechargeable lithium batteries
journal, July 2001

Lithium deintercalation in LiFePO4 nanoparticles via a domino-cascade model
journal, July 2008

Phase Change in Li[sub x]FePO[sub 4]
journal, January 2005

Discharge Model for the Lithium Iron-Phosphate Electrode
journal, January 2004

Phospho-olivines as Positive-Electrode Materials for Rechargeable Lithium Batteries
journal, April 1997

Size-Dependent Lithium Miscibility Gap in Nanoscale Li[sub 1−x]FePO[sub 4]
journal, January 2007

Room-temperature single-phase Li insertion/extraction in nanoscale LixFePO4
journal, July 2008

Suppression of Phase Separation in LiFePO ₄ Nanoparticles During Battery Discharge
journal, November 2011

Dynamic Solubility Limits in Nanosized Olivine LiFePO ₄
journal, July 2011

Isolation of Solid Solution Phases in Size-Controlled Li x FePO ₄ at Room Temperature
journal, February 2009

Coherency Strain and the Kinetics of Phase Separation in LiFePO ₄ Nanoparticles
journal, February 2012

Study of the Li-insertion/extraction process in LiFePO4/FePO4
journal, February 2009

Study of the LiFePO ₄ /FePO ₄ Two-Phase System by High-Resolution Electron Energy Loss Spectroscopy
journal, November 2006

Electron Microscopy Study of the LiFePO[sub 4] to FePO[sub 4] Phase Transition
journal, January 2006

Size-Dependent Spinodal and Miscibility Gaps for Intercalation in Nanoparticles
journal, November 2009

Electrochemically Induced Phase Transformation in Nanoscale Olivines Li _{1− x} MPO ₄ (M = Fe, Mn)
journal, October 2008

Elastic properties of olivine ${Li}_{x} {FePO}_{4}$ from first principles
journal, May 2006

The Role of Surface and Interface Energy on Phase Stability of Nanosized Insertion Compounds
journal, April 2009

Anisotropic Phase Boundary Morphology in Nanoscale Olivine Electrode Particles
journal, February 2011

Metastable Solid-Solution Phases in the LiFePO[sub 4]∕FePO[sub 4] System
journal, January 2007

Mesoscale Phase Distribution in Single Particles of LiFePO ₄ following Lithium Deintercalation
journal, April 2013

Spectroscopic studies of ${Li}_{x} Fe P O_{4}$ and ${Li}_{x} M_{0.03} {Fe}_{0.97} P O_{4}$ $(M = Cr, Cu, Al, Ti)$
journal, July 2005

Effect of surface energies and nano-particle size distribution on open circuit voltage of Li-electrodes
journal, April 2009

Surface effects on electrochemical properties of nano-sized LiFePO4
journal, January 2011

Relationship between local structure and electrochemical performance of LiFePO4 in Li-ion batteries
journal, December 2007

IR Near-Field Spectroscopy and Imaging of Single Li _x FePO ₄ Microcrystals
journal, December 2014

First-principles study of surface properties of $Li Fe P O_{4}$ : Surface energy, structure, Wulff shape, and surface redox potential
journal, October 2007

Theory of Coherent Nucleation in Phase-Separating Nanoparticles
journal, May 2013

Intercalation dynamics in rechargeable battery materials: General theory and phase-transformation waves in LiFePO4
journal, November 2008

Phase Separation Dynamics in Isotropic Ion-Intercalation Particles
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
journal, April 2013

Finite element model of ionic nanowires with size-dependent mechanical properties determined by ab initio calculations
journal, January 2011

Phase Field Theory of Heterogeneous Crystal Nucleation
journal, January 2007

Theory of Chemical Kinetics and Charge Transfer based on Nonequilibrium Thermodynamics
journal, June 2012

Critical point wetting
journal, April 1977

Elastically constrained phase-separation dynamics competing with the charge process in the LiFePO4/FePO4 system
journal, January 2013

The thermodynamic origin of hysteresis in insertion batteries
journal, April 2010

Phase Transformation Dynamics in Porous Battery Electrodes
journal, November 2014

Configurational Electronic Entropy and the Phase Diagram of Mixed-Valence Oxides: The Case of ${Li}_{x} {FePO}_{4}$
journal, October 2006

Kinetics of non-equilibrium lithium incorporation in LiFePO4
journal, July 2011

Model for the Particle Size, Overpotential, and Strain Dependence of Phase Transition Pathways in Storage Electrodes: Application to Nanoscale Olivines
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
journal, November 2004

Composition, structure, and stability of ${RuO}_{2} (110)$ as a function of oxygen pressure
journal, December 2001

Size-dependent elastic properties of nanosized structural elements
journal, July 2000

Efficient Management of Parallelism in Object-Oriented Numerical Software Libraries
book, January 1997

Automated Solution of Differential Equations by the Finite Element Method
book, January 2012

A compiler for variational forms
journal, September 2006

Gmsh: A 3-D finite element mesh generator with built-in pre- and post-processing facilities
journal, September 2009

A phase-field study of the effect of local deformation velocity on lithiation-induced stress in wire-like structures
journal, February 2019

Phase Field Modeling of Coupled Phase Separation and Diffusion-Induced Stress in Lithium Iron Phosphate Particles Reconstructed From Synchrotron Nano X-ray Tomography
journal, April 2019

Three-dimensional localization of nanoscale battery reactions using soft X-ray tomography
journal, March 2018

Multiphase Porous Electrode Theory
journal, January 2017

Toward Optimal Performance and In-Depth Understanding of Spinel Li ₄ Ti ₅ O ₁₂ Electrodes through Phase Field Modeling
journal, February 2018

Phase-field study of surface irregularities of a cathode particle during intercalation
journal, August 2018

An Extended Formulation of Butler-Volmer Electrochemical Reaction Kinetics Including the Influence of Mechanics
journal, January 2019

Phase transformation and fracture in single Li _x FePO ₄ cathode particles: a phase-field approach to Li–ion intercalation and fracture
journal, March 2016

Three-dimensional localization of nanoscale battery reactions using soft X-ray tomography.
text, January 2018

Three-dimensional localization of nanoscale battery reactions using soft X-ray tomography.
text, January 2018