Understanding the Roles of the Electrode/Electrolyte Interface for Enabling Stable Li∥Sulfurized Polyacrylonitrile Batteries.

Sulfurized polyacrylonitrile (SPAN) is a promising high-capacity cathode material. In this work, we use spatially resolved X-ray absorption spectroscopy combined with X-ray fluorescence (XRF) microscopy, X-ray photoelectron spectroscopy, and scanning electron microscopy to examine the structural transformation of SPAN and the critical role of a robust cathode-electrolyte interface (CEI) on the electrode. LiS species forms during the cycling of SPAN. However, in carbonate-based electrolytes and ether-based electrolytes with LiNO additives, these species are well protected by the CEI and do not dissolve into the electrolytes. In contrast, in an ether-based electrolyte without the LiNO additive, LiS species dissolve into the electrolyte, resulting in the shuttle effect and capacity loss. Examination of the Li anode by XRF and SEM reveals dense spherical Li morphology in ether-based electrolytes, but sulfur is present in the absence of the LiNO additive. In contrast, porous dendritic Li is found in the carbonate electrolyte. These analyses established that an ether-based electrolyte with LiNO is a superior choice that enables stable cycling of both electrodes. Based on these insights, we successfully demonstrate the stable cycling of high areal loading SPAN cathode (>6.5 mA h cm) with lean electrolyte amounts, showing promising Li∥SPAN cell performance under practical conditions.