Slurry‐Fabricable Li+‐Conductive Polymeric Binders for Practical All‐Solid‐State Lithium‐Ion Batteries Enabled by Solvate Ionic Liquids

Abstract For mass production of all‐solid‐state lithium‐ion batteries (ASLBs) employing highly Li + conductive and mechanically sinterable sulfide solid electrolytes (SEs), the wet‐slurry process is imperative. Unfortunately, the poor chemical stability of sulfide SEs severely restrict available candidates for solvents and in turn polymeric binders. Moreover, the binders interrupt Li + ‐ionic contacts at interfaces, resulting in the below par electrochemical performance. In this work, a new scalable slurry fabrication protocol for sheet‐type ASLB electrodes made of Li + ‐conductive polymeric binders is reported. The use of intermediate‐polarity solvent (e.g., dibromomethane) for the slurry allows for accommodating Li 6 PS 5 Cl and solvate‐ionic‐liquid‐based polymeric binders (NBR‐Li(G3)TFSI, NBR: nitrile−butadiene rubber, G3: triethylene glycol dimethyl ether, LiTFSI: lithium bis(trifluoromethanesulfonyl)imide) together without suffering from undesirable side reactions or phase separation. The LiNi 0.6 Co 0.2 Mn 0.2 O 2 and Li 4 Ti 5 O 12 electrodes employing NBR‐Li(G3)TFSI show high capacities of 174 and 160 mA h g −1 at 30 °C, respectively, which are far superior to those using conventional NBR (144 and 76 mA h g −1 ). Moreover, high areal capacity of 7.4 mA h cm −2 is highlighted for the LiNi 0.7 Co 0.15 Mn 0.15 O 2 electrodes with ultrahigh mass loading of 45 mg cm −2 . The facilitated Li + ‐ionic contacts at interfaces paved by NBR‐Li(G3)TFSI are evidenced by the complementary analysis from electrochemical and 7 Li nuclear magnetic resonance measurements.