Particle size dependent confinement and lattice strain effects in LiFePO4

We report the intrinsic electronic properties of LiFePO4 (LFP) with different particle sizes measured by broad-band impedance spectroscopy and diffuse reflectance spectroscopy. The electronic properties show typical size-dependent effects with decreasing particle size (up to 150 nm). However, at the nanoscale level, we observed an enhancement in the polaronic conductivity about an order of magnitude. We found that the origin of the enhanced electronic conductivity in LFP is due to the significant lattice strain associated with the reduction of particle size. The observed lattice strain component corresponds to the compressive part which leads to a decrease in the hopping length of the polarons. We reproduce nonlinearities in the transport properties of LFP with particle size, to capture the interplay between confinement and lattice strain, and track the effects of strain on the electron-phonon interactions. These results could explain why nano-sized LFP has a better discharge capacity and higher rate capability than the bulk counterpart. We suggest that these new correlations will bring greater insight and better understanding for the optimization of LFP as a cathode material for advanced lithium ion batteries.