Effects of Imide–Orthoborate Dual-Salt Mixtures in Organic Carbonate Electrolytes on the Stability of Lithium Metal Batteries

The effects of lithium imide and lithium orthoborate dual-salt electrolytes of different salt chemistries in carbonate solvents on the cycling stability of lithium (Li) metal batteries are systematically and comparatively investigated. Two imide salts (LiTFSI and LiFSI) and two orthoborate salts (LiBOB and LiDFOB) are chosen for this study and compared with the conventional LiPF6 salt. Density functional theory calculations indicate that the chemical and electrochemical stabilities rank in the following order: LiTFSI-LiBOB > LiTFSI-LiDFOB > LiFSI-LiDFOB > LiFSI-LiBOB. The experimental cycling stability of the Li metal batteries with the electrolytes ranks in the following order: LiTFSI-LiBOB > LiTFSI-LiDFOB > LiFSI-LiDFOB > LiPF6 > LiFSI-LiBOB, which is in well accordance with the calculation results. The LiTFSI-LiBOB can effectively protect the Al substrate and form a more robust surface film on Li metal anode, while the LiFSI-LiBOB results in serious corrosion to the stainless steel cell case and a thicker and looser surface film on Li anode. The key findings of this work emphasize that the salt chemistry is critically important for enhancing the interfacial stability of Li metal anode and should be carefully manipulated in the development of high-performance Li metal batteries