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

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-LiFePO₄ (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_1/3Co_1/3Mn_1/3O₂ (NMC111) and Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ (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.