Excess Li-ion storage on reconstructed surfaces of nanocrystals to boost battery performance

Because of their enhanced kinetic properties, nanocrystallites have received much attention as potential electrode materials for energy storage. However, because of the large specific surface areas of nanocrystallites, they usually suffer from decreased energy density, cycling stability, and effective electrode capacity. In this work, we report a size-dependent excess capacity beyond theoretical value (170 mA h g–1) by introducing extra lithium storage at the reconstructed surface in nanosized LiFePO4 (LFP) cathode materials (186 and 207 mA h g–1 in samples with mean particle sizes of 83 and 42 nm, respectively). Moreover, this LFP composite also shows excellent cycling stability and high rate performance. Our multimodal experimental characterizations and ab initio calculations reveal that the surface extra lithium storage is mainly attributed to the charge passivation of Fe by the surface C–O–Fe bonds, which can enhance binding energy for surface lithium by compensating surface Fe truncated symmetry to c...