Dry‐Processed LiNi _0.6 Co _0.2 Mn _0.2 O ₂ Cathode via Solid‐State Electrolyte‐Assisted Calendering

Polytetrafluoroethylene (PTFE)–fibrillated dry processing offers a solvent‐free and scalable route for fabricating lithium‐ion battery cathodes. The calendering process inherent to PTFE‐fibrillated dry processing, however, involves coupled shear and compaction that critically govern electrode microstructure and performance. Herein, we map the microstructure–performance evolution of PTFE‐fibrillated LiNi 0 . 6 Co 0 . 2 Mn 0 . 2 O 2 (NCM) cathodes. The results reveal that the calendering process introduces extensional deformation that disrupts the internal pore network, impairing lithium‐ion transport and capacity retention of NCM cathode. Incorporation of Li 1 . 3 Al 0 . 3 Ti 1 . 7 (PO 4 ) 3 (LATP) solid‐state electrolyte nanoparticles into the dry electrode matrix effectively maintains electrode porosity during compression and enhance electrochemical performance. The LATP nanoparticle‐assisted calendering reduces pore size and diffusion resistance, thereby improving lithium‐ion transport kinetics. As a result, the LATP‐NCM cathode demonstrated improved specific discharge capacities across various mass loadings. Even with a high mass loading of 41 mg cm −2 , the LATP‐NCM cathode exhibited a high specific capacity of 174.4 mAh g −1 and an areal capacity of 7.2 mAh cm −2 . This work clarifies the processing‐microstructure‐transport nexus in dry‐processed electrodes and provides key insights for scalable fabrication of high‐performance dry electrodes.