Superlithiation Performance of Pyridinium Polymerized Ionic Liquids with Fast Li⁺ Diffusion Kinetics as Anode Materials for Lithium‐Ion Battery

Abstract Polymerized ionic liquids (PILs) with super ion diffusion kinetics have aroused considerable attention in rechargeable batteries, which are very promising to solve the problem of the slow ion diffusion kinetics in organic electrode materials. Theoretically, PILs incorporated redox groups are very suitable as anode materials to realize “superlithiation” performance, achieving high lithium storage capacity. In this study, redox pyridinium‐based PILs (PILs‐Py‐400) have been synthesized through trimerization reactions by pyridinium ionic liquids with cyano groups under an appropriate temperature (400 °C). The positively charged skeleton, extended conjugated system, abundant micropores, and amorphous structure for PILs‐Py‐400 can boost the utilization efficiency of redox sites. A high capacity of 1643 mAh g⁻¹ at 0.1 A g⁻¹ (96.7% of the theoretical capacity) has been obtained, indicating intriguing 13 Li⁺ redox reactions in per repeating unit of one pyridinium ring, one triazine ring, and one methylene. Moreover, PILs‐Py‐400 exhibit excellent cycling stability with a capacity of around 1100 mAh g⁻¹ at 1.0 A g⁻¹ after 500 cycles, and the capacity retention is 92.2%.