Evaluating the impact of additives and lithium salts on the performance of spinel cathode material LiMn2O4

Abstract

LiMn2O4 spinel structure was considered as the cathode material to replace LiCoO2 for high voltage lithium-ion batteries, however, its main drawback was poor cycling due to dissolution of manganese and structural instability. One of the effective solutions is to find out a suitable electrolyte composition and additive to reduce the manganese dissolution and to prevent the side reaction between the electrode material and the electrolyte. In this study, we investigated the impact of using fluoroethylene carbonate (FEC), vinyl carbonate (VC), lithium bis(oxalato)borate (LiBOB) as additives for the electrolyte of 1 M LiPF6/EC:DMC (1:1) and different salt such as: LiBF4, LiClO4 and LiTFSI for commercial carbonate solvent of EC:DMC (1:1) on the improvement of the cyclic stability and electrochemical performance of LiMn2O4 electrodes. The results showed that the addition of FEC did not affect the initial capacity but increased significantly the cycle stability of the material. In particular, the discharge capacity maintained 91% of initial value after 20 cycles in the electrolytes containing 2 %wt and 3 %wt FEC, respectively. However, further increase of FEC content induced the polarization of the charge discharge curves as well as the increase of the electrode - electrolyte interface resistance which were responsible for the cycling performance decline. Among tested salts, LiClO4 was the best electrolytic one for EC:DMC (1:1) based-electrolyte that enhanced the initial discharge capacity roughly 20 mAh/g. In addition, preliminary results on the full-cell of graphite||LMO achieved the discharge capacity of 87.09 mAh/g (at C/5) and 73.52 mAh/g (at C/2) which is about 66.99 % the initial discharge capacity obtained at C/5 of the half-cell LMO|Li).