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Using mathematical model for intercalation dynamics in phase-separatingmaterials proposed in (Singh, G. K.; Ceder, G.; Bazant, M. Z. ElectrochimicaActa 2008, 53, 7599) and developed further in (Burch, D.; Bazant, M. Z. NanoLetters 2009, 9, 3795) we found that the spinodal gap generally shrinks as theparticle size decreases. We also got that for some range of boundary reactionrate parameter and particle size the concentration spinodal gap is notcontinuous but it has stable "islands" where no spinodal decomposition isexpected. In fact the presence of infinitesimally small boundary reaction rateparameter will destabilize nano particle even for infinitesimal length ofparticle. But then further continuous raise of this parameter will stabilizethe system till some limit. We made careful analysis to study the dependence ofspinodal decomposition on boundary reaction rate and size parameters which canbe used for LiFePO4 battery material application. Our model predicted that fornanoparticles having size less than diffusion length and enough small boundaryreaction rate spontanious charge or discharge will occur.

Spinodal Gap Dependence on Size and Boundary Reaction Rate for Intercalation in Nanoparticles