Electrochemically Driven Phase Transitions in Insertion Electrodes for Lithium-Ion Batteries: Examples in Lithium Metal Phosphate Olivines
- 1 June 2010
- journal article
- Published by Annual Reviews in Annual Review of Materials Research
- Vol. 40 (1), 501-529
- https://doi.org/10.1146/annurev-matsci-070909-104435
Abstract
The thermodynamics and kinetics of phase transformations in electrochemical systems are reviewed. Phase transitions in LiMPO4(M = Fe, Mn, Ni, Co) olivines are highlighted. The phase transformation phenomena in LiMPO4are diverse and include thermodynamic effects of particle size and applied overpotential, the appearance of metastable phases, and the effects of defects from atomic disorder and aliovalent doping. Such phenomena also include kinetic effects such as interface motion and diffusion of Li-electron complexes. The nature of phase transitions directly influences electrode performance in battery applications. Reduced particle size and doping can reduce or eliminate room-temperature Li miscibility gaps, which in turn affect characteristics of state of charge versus voltage and the elastic energy due to volume mismatches between phases. Near the conditions for a phase transition, Li diffusion coefficients are reduced. Nucleation and growth kinetics produce a series of phase transition sequences, which can result in the accumulation of noncrystalline phases during electrochemical cycling.Keywords
This publication has 85 references indexed in Scilit:
- Electrochemically Induced Phase Transformation in Nanoscale Olivines Li1−xMPO4 (M = Fe, Mn)Chemistry of Materials, 2008
- Intercalation dynamics in rechargeable battery materials: General theory and phase-transformation waves in LiFePO4Electrochimica Acta, 2008
- Surface structures and crystal morphologies of LiFePO4: relevance to electrochemical behaviourJournal of Materials Chemistry, 2008
- Market watchNature, 2006
- Diffuse interface model for structural transitions of grain boundariesPhysical Review B, 2006
- Apparent diffusion coefficient of intercalated species measured with PITTElectrochimica Acta, 2005
- Comparison between Cottrell diffusion and moving boundary models for determination of the chemical diffusion coefficients in ion-insertion electrodesElectrochimica Acta, 2005
- Relating atomistic grain boundary simulation results to the phase-field modelComputational Materials Science, 2002
- Phase transformations and volume changes in spinel LixMn2O4Solid State Ionics, 2000
- Diffusion Coefficients of Lithium Ions during Intercalation into Graphite Derived from the Simultaneous Measurements and Modeling of Electrochemical Impedance and Potentiostatic Intermittent Titration Characteristics of Thin Graphite ElectrodesThe Journal of Physical Chemistry B, 1997