Self‐Catalyzed Exothermic Binder Enables Ultrafast Processing and Migration‐Resistant Binder Networks for High‐Performance Lithium Battery Cathodes

Abstract

Abstract Scalable manufacturing of high‐performance cathodes is crucial for next‐generation lithium‐ion batteries (LIBs). However, conventional binders such as polyvinylidene fluoride (PVDF) require prolonged drying, which slows electrode production and induces binder migration. Herein, we report a self‐catalyzed exothermic resin (ExoR) binder that undergoes rapid, thermally triggered polymerization, completing network cross‐linking within 3 min while consuming 70% less drying energy than PVDF. Thermal and microstructural analyses confirm rapid ExoR polymerization and complete solvent removal, while revealing a uniform binder distribution and a continuous carbon‐binder domain. This architecture lowers interfacial resistance and restrains polarization, producing an enhanced electrochemical response. The ExoR‐LiFePO 4 (LFP) cathode achieves a near‐theoretical specific capacity at 0.1 C and excellent cycling stability, maintaining 155 mAh g −1 with 95.5% retention after 500 cycles. Furthermore, high‐mass‐loading (20 mg cm −2 ) ExoR‐LFP cathodes deliver 2.4 mAh cm −2 areal capacity while preserving structural integrity. The ExoR binder also performs well with LiNi 1/3 Co 1/3 Mn 1/3 O 2 (NMC111) and Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 (LMRO) cathodes, demonstrating broad compatibility across diverse chemistries. By concurrently improving manufacturing efficiency and electrochemical performance, this nearly fluorine‐free (0.05 wt.%) ExoR system provides a scalable and sustainable strategy for the high‐throughput production of advanced lithium‐ion cathodes.