LiCoO2/Graphite Cells with Localized High Concentration Carbonate Electrolytes for Higher Energy Density

Widening the working voltage of lithium-ion batteries is considered as an effective strategy to improve their energy density. However, the decomposition of conventional aprotic electrolytes at high voltage greatly impedes the success until the presence of high concentration electrolytes (HCEs) and the resultant localized HCEs (LHCEs). The unique solvated structure of HCEs/LHCEs endows the involved solvent with enhanced endurance toward high voltage while the LHCEs can simultaneously possess the decent viscosity for sufficient wettability to porous electrodes and separator. Nowadays, most LHCEs use LiFSI/LiTFSI as the salts and β-hydrofluoroethers as the counter solvents due to their good compatibility, yet the LHCE formula of cheap LiPF6 and high antioxidant α-hydrofluoroethers is seldom investigated. Here, we report a unique formula with 3 mol L−1 LiPF6 in mixed carbonate solvents and a counter solvent α-substituted fluorine compound (1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropylether). Compared to a conventional electrolyte, this formula enables dramatic improvement in the cycling performance of LiCoO2//graphite cells from approximately 150 cycles to 1000 cycles within the range of 2.9 to 4.5 V at 0.5 C. This work provides a new choice and scope to design functional LHCEs for high voltage systems.