Complementary Electrolyte Design for Li Metal Batteries in Electric Vehicle Applications

A complementary electrolyte system with 0.8 M lithium bis(fluorosulfonylimide) (LiFSI) salt and 2 wt % lithium perchlorate (LiClO₄) additive in fluoroethylene carbonate (FEC)/ethyl methyl carbonate (EMC) solution enables not only stable cycling of lithium metal batteries (LMBs) with practical loading (<30 μm lithium anode, cathode loading > 4 mAh/cm²) but also outstanding degradation stability toward the end of cycle life when compared to the conventional electrolyte. Although the use of LiFSI salt can increase the electrolyte conductivity and lengthen the cycle life of LMBs, the aged lithium anode morphology formed by the sacrificial decomposition of LiFSI is highly porous, leading to an abrupt cell capacity drop toward the end of cycling. Moreover, the inability to stop aluminum corrosion by the LiFSI-based electrolyte also causes cracking of the cathode tab during prolonged cycling. It is observed that a highly porous aged lithium consumed electrolyte at a higher rate, leading to the dry-out of electrolyte solvents. On the contrary, dense aged lithium anode morphology increased the localized current applied on the lithium, causing the formation of lithium dendrite. Thus, porosity control is the key to enhance battery performance. In this complementary system, LiClO₄ was introduced as an advanced additive to not only improve the capacity retention rate but also mitigate the abrupt capacity drop toward the end of cycle life because LiClO₄ acted as a pore astringent reducing the porosity of the aged lithium metal anode to the desired level. Moreover, the addition of LiClO₄ can also suppress the Al corrosion, allowing stable high-voltage cycling of LMBs. The synergistic effect of combining LiFSI salt and a LiClO₄ additive leads to an electrolyte system that can facilitate the application of high-energy LMBs with practical electrode loading.