Long-Term Stable Lithium Metal Anode in Highly Concentrated Sulfolane-Based Electrolytes with Ultrafine Porous...

Highly concentrated solutions composed of lithium bis(fluorosulfonyl)imide (LiFSI) and sulfolane (SL) are promising liquid electrolytes for lithium metal batteries because of their high anodic stability, low flammability, and high compatibility with lithium metal anodes. However, it is still challenging to obtain the stable lithium metal anodes in the concentrated electrolytes due to their poor wettability to the conventional polyolefin separators. Here, we report that the highly concentrated 1:2.5 LiFSI/SL electrolyte coupled with a three-dimensionally ordered macroporous polyimide (3DOM PI) separator enables the stable lithium plating/stripping cycling with an average Coulombic efficiency of ca. 98% for over 400 cycles at 1.0 mA cm^-2. The 3DOM PI separator shows good electrolyte wettability and large electrolyte uptake due to its high porosity and polar constituent of the imide structure, allowing superior cycling performance in the highly concentrated solution, compared with the polyolefin separators. Electrochemical and spectroscopic analyses reveal that the superior cycling stability in the concentrated electrolyte is attributed to the formation of highly stable and Li⁺ ion conductive solid electrolyte interphase (SEI) layer derived from FSI^- anions, which reduces the side reactions of SL with lithium metal, prevents the growth of lithium dendrites, and suppresses the increase in cell impedance over long-term cycling. Our findings demonstrate that polar and porous separators could effectively improve the affinity to the concentrated electrolytes and allow the formation of the anion-derived SEI layer by increasing the salt concentration of the electrolytes, achieving the long-term stable lithium metal anode.