A review of recent research on nonequilibrium solid solution behavior in LiXFePO4 [A review of nonequilibrium solid solution in LiXFePO4]

doi:10.1016/j.ssi.2018.05.026

Title: A review of recent research on nonequilibrium solid solution behavior in Li _XFePO ₄ [A review of nonequilibrium solid solution in Li _XFePO ₄]

Full Record
Other Related Research

Abstract

Li _XFePO ₄ (0 < X < 1) is one of the most well-studied cathode battery materials and is notable for its large miscibility gap. Although its phase-separating behaviors under equilibrium conditions have been well documented, recent research has shown that phase separation is suppressed at elevated rates of lithium insertion and removal. Specifically, Li _XFePO ₄ exhibits a nonequilibrium solid solution behavior at elevated cycling rates. This article reviews recent research on nonequilibrium solid solution in Li _XFePO ₄; these insights have been largely enabled by operando characterization techniques. As a result, such studies have not only unambiguously confirmed the existence of this solid solution, but also show how surface reaction and diffusion kinetics ultimately affect phase separation and other spatially nonuniform lithiation and delithiation behavior.

Authors:

Li, Yiyang ^[1]

Sandia National Lab. (SNL-CA), Livermore, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)

Publication Date:: 2018-06-01

Research Org.:: Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

Sponsoring Org.:: USDOE National Nuclear Security Administration (NNSA)

OSTI Identifier:: 1477467

Report Number(s):: SAND-2018-2020J
Journal ID: ISSN 0167-2738; 660930

Grant/Contract Number:: AC04-94AL85000

Resource Type:: Accepted Manuscript

Journal Name:: Solid State Ionics

Additional Journal Information:: Journal Volume: 323; Journal Issue: C; Journal ID: ISSN 0167-2738

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE; LiFePO4; Phase transformation; Solid solution; Operando characterization

Citation Formats


                    Li, Yiyang. A review of recent research on nonequilibrium solid solution behavior in LiXFePO4 [A review of nonequilibrium solid solution in LiXFePO4].  United States: N. p., 2018. 
        Web.  doi:10.1016/j.ssi.2018.05.026.

Copy to clipboard


                    Li, Yiyang. A review of recent research on nonequilibrium solid solution behavior in LiXFePO4 [A review of nonequilibrium solid solution in LiXFePO4].  United States.  doi:10.1016/j.ssi.2018.05.026.

Copy to clipboard


                    Li, Yiyang. Fri .  
        "A review of recent research on nonequilibrium solid solution behavior in LiXFePO4 [A review of nonequilibrium solid solution in LiXFePO4]".  United States.  doi:10.1016/j.ssi.2018.05.026.  https://www.osti.gov/servlets/purl/1477467.

Copy to clipboard


                    
@article{osti_1477467,

  title        = {A review of recent research on nonequilibrium solid solution behavior in LiXFePO4 [A review of nonequilibrium solid solution in LiXFePO4]},

  author       = {Li, Yiyang},

  abstractNote = {LiXFePO4 (0 < X < 1) is one of the most well-studied cathode battery materials and is notable for its large miscibility gap. Although its phase-separating behaviors under equilibrium conditions have been well documented, recent research has shown that phase separation is suppressed at elevated rates of lithium insertion and removal. Specifically, LiXFePO4 exhibits a nonequilibrium solid solution behavior at elevated cycling rates. This article reviews recent research on nonequilibrium solid solution in LiXFePO4; these insights have been largely enabled by operando characterization techniques. As a result, such studies have not only unambiguously confirmed the existence of this solid solution, but also show how surface reaction and diffusion kinetics ultimately affect phase separation and other spatially nonuniform lithiation and delithiation behavior.},

  doi          = {10.1016/j.ssi.2018.05.026},

  journal      = {Solid State Ionics},

  number       = C,

  volume       = 323,

  place        = {United States},

  year         = {2018},

  month        = {6}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

DOI: 10.1016/j.ssi.2018.05.026

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 1 work

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Similar Records in DOE PAGES and OSTI.GOV collections:

Nanoscale Detection of Intermediate Solid Solutions in Equilibrated Li _xFePO ₄ Microcrystals

Journal Article May, Brian M. ; Yu, Young-Sang ; Holt, Martin V. ; ... - Nano Letters

Redox-driven phase transformations in solids determine the performance of lithium-ion batteries, crucial in the technological transition from fossil fuels. Couplings between chemistry and strain define reversibility and fatigue of an electrode. The accurate definition of all phases in the transformation, their energetics, and nanoscale location within a particle produces fundamental understanding of these couplings needed to design materials with ultimate performance. In this paper we demonstrate that scanning X-ray diffraction microscopy (SXDM) extends our ability to image battery processes in single particles. In LiFePO ₄ crystals equilibrated after delithiation, SXDM revealed the existence of domains of miscibility between LiFePO ₄more »« less
Cited by 4
DOI: 10.1021/acs.nanolett.7b03086

Full Text Available
Phase-field modeling of diffusional phase behaviors of solid surfaces: A case study of phase-separating Li _XFePO ₄ electrode particles

Journal Article Heo, Tae Wook ; Chen, Long-Qing ; Wood, Brandon C. - Computational Materials Science

In this paper, we present a comprehensive phase-field model for simulating diffusion-mediated kinetic phase behaviors near the surface of a solid particle. The model incorporates elastic inhomogeneity and anisotropy, diffusion mobility anisotropy, interfacial energy anisotropy, and Cahn–Hilliard diffusion kinetics. The free energy density function is formulated based on the regular solution model taking into account the possible solute-surface interaction near the surface. The coherency strain energy is computed using the Fourier-spectral iterative-perturbation method due to the strong elastic inhomogeneity with a zero surface traction boundary condition. Employing a phase-separating Li _XFePO ₄ electrode particle for Li-ion batteries as a modelmore »« less
Cited by 2
DOI: 10.1016/j.commatsci.2015.03.020

Full Text Available
Miscibility Gap Closure, Interface Morphology, and Phase Microstructure of 3D Li _xFePO ₄ Nanoparticles from Surface Wetting and Coherency Strain

Journal Article Welland, Michael J. ; Karpeyev, Dmitry ; O’Connor, Devin T. ; ... - ACS Nano

We study the mesoscopic effects which suppress phase-segregation in Li _xFePO ₄ 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 ofmore »« less
Cited by 20
DOI: 10.1021/acsnano.5b02555

Full Text Available
Dependence on Crystal Size of the Nanoscale Chemical Phase Distribution and Fracture in Li _xFePO ₄

Journal Article Yu, Young-Sang ; Kim, Chunjoong ; Shapiro, David A. ; ... - Nano Letters

The performance of battery electrode materials is strongly affected by inefficiencies in utilization kinetics and cycle life as well as size effects. Observations of phase transformations in these materials with high chemical and spatial resolution can elucidate the relationship between chemical processes and mechanical degradation. Soft X-ray ptychographic microscopy combined with X-ray absorption spectroscopy and electron microscopy creates a powerful suite of tools that we use to assess the chemical and morphological changes in lithium iron phosphate (LiFePO ₄) micro- and nanocrystals that occur upon delithiation. All sizes of partly delithiated crystals were found to contain two phases with amore »« less
Cited by 35
DOI: 10.1021/acs.nanolett.5b01314

Full Text Available
Crystal Chemistry and Electrochemistry of Li _xMn _1.5Ni _0.5O ₄ Solid Solution Cathode Materials

Journal Article Kan, Wang Hay ; Kuppan, Saravanan ; Cheng, Lei ; ... - Chemistry of Materials

For ordered high-voltage spinel LiMn _1.5Ni _0.5O ₄ (LMNO) with the P4 ₃2 ₁ symmetry, the two consecutive two-phase transformations at ~4.7 V (vs Li ⁺/Li), involving three cubic phases of LMNO, Li _0.5Mn _1.5Ni _0.5O ₄ (L _0.5MNO), and Mn _1.5Ni _0.5O ₄ (MNO), have been well-established. Such a mechanism is traditionally associated with poor kinetics due to the slow movement of the phase boundaries and the large mechanical strain resulting from the volume changes among the phases, yet ordered LMNO has been shown to have excellent rate capability. In this paper, we show the ability of the phasesmore »« less
Cited by 1
DOI: 10.1021/acs.chemmater.7b01898

Full Text Available

Similar Records

Title: A review of recent research on nonequilibrium solid solution behavior in Li XFePO 4 [A review of nonequilibrium solid solution in Li XFePO 4]

Abstract

Citation Formats

Title: A review of recent research on nonequilibrium solid solution behavior in Li _XFePO ₄ [A review of nonequilibrium solid solution in Li _XFePO ₄]