Plasticizers of poly(ethylene glycol)-borate (PEG-B) esters are added into lithium-conducting gel polymer electrolyte (GPE) in Li-S cells in order to inhibit the unrestrained migration of polysulfide anions. An improvement of the electrochemical properties of the Li-S cell using GPE is observed upon addition of the plasticizers at room temperature. However, a slow decrease of discharge capacities follows after stable cycles. To understand the origin of the capacity fading, electrochemical impedance spectroscopies (EIS), scanning electron microscopy (SEM), X-ray Diffraction (XRD) and X-ray photoelectron spectra (XPS) are adopted. EIS measurements indicate that the decrease of capacity in the Li-S cell using GPE is related to the increase of interfacial resistance between GPE and anode. SEM studies combined with XRD and XPS measurements reveal the increase of interfacial resistance between GPE and anode is results from Li2S corrosion products. Accordingly, the polysulfide anions precipitate on the anode surface, which leads to a reduction of the cycle life of the Li-S cell using GPE. Li-ion transference number measurement shows an increase of transference number before 20th cycles, and then decreased, which suggests that the GPE using PEG-B esters as plasticizers could inhibit the unrestrained migration of polysulfide anions at some time but not permanently. (C) 2013 Elsevier B.V. All rights reserved.