Atomic-scale structural and chemical evolution of Li3V2(PO4)3 cathode cycled at high voltage window
lithium-ion batteries, Li-deficient lithium vanadium phosphate, capacity fading, solid electrolyte interphase, scanning transmission electron microscopy, electron energy loss spectroscopy
Here, by using atomically resolved scanning transmission electron microscopy and electron energy loss spectroscopy, we investigate the structural and chemical evolution of Li3V2(PO4)3 (LVP) upon the high-voltage window (3.0–4.8 V). We find that the valence of vanadium gradually increases towards the core corresponding to the formation of electrochemically inactive Li3−xV2(PO4)3 (L3−xVP) phases. These Li-deficient phases exhibit structure distortion with superstructure stripes, likely caused by the migration of the vanadium, which can slow down the lithium ion diffusion or even block the diffusion channels. Such kinetic limitations lead to the formation of Li-deficient phase along with capacity loss. Thus, the LVP continuously losses of electrochemical activity and Li-deficient phases gradually grow from the particle core towards the surface during cycling. After 500 cycles, the thickness of active LVP layer decreases to be ~ 5–20 nm. Moreover, the micromorphology and chemical composition of solid electrolyte interphase (SEI) have been investigated, indicating the thick SEI film also contributes to the capacity loss. The present work reveals the structural and chemical evolution in the cycled electrode materials at an atomic scale, which is essential to understand the voltage fading and capacity decaying of LVP cathode.
Tsinghua University Press
Shulin Chen,Jian Zou,Yuehui Li,Ning Li,Mei Wu,Jinghuang Lin,Jingmin Zhang,Jian Cao,Jicai Feng,Xiaobin Niu,Jianming Bai,Junlei Qi,Peng Gao,Liping Wang,Hong Li, Atomic-scale structural and chemical evolution of Li3V2(PO4)3 cathode cycled at high voltage window. NanoRes.2019, 12(7): 1675–1681