Towards a High-Performance Lithium-Metal Battery with Glyme Solution and an Olivine Cathode

High‐performance lithium‐metal batteries are achieved by using a glyme‐based electrolyte enhanced with a LiNO3 additive and a LiFePO4 cathode. An optimal electrolyte formulation is selected upon detailed analysis of the electrochemical properties of various solutions formed by dissolving respectively lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), and lithium bis(pentafluoroethanesulfonyl)imide (LiBETI) either in diethylene glycol dimethyl ether or in triethylene glycol dimethyl ether and by adding LiNO3. A thorough investigation shows evidence of efficient ionic transport, a wide stability window, low reactivity with lithium metal, and cathode/electrolyte interphase characteristics that are strongly dependent on the glyme chain length. The best Li/LiFePO4 battery delivers 154 mAh g−1 at C/3 (1 C=170 mA g−1) without any decay after 200 cycles. Tests at 1 C and 5 C show initial capacities of about 150 and 140 mAh g−1, a retention exceeding 70 % after 500 cycles, and suitable electrode/electrolyte interphases evolution.