• • LATP@C nanofiber network enables dry-processed NCM811 cathodes with areal loading up to 100 mg cm−2, delivering 203 mA h g−1 at 0.1 C and retaining 96.7% capacity after 35 cycles at 0.2 C, demonstrating feasibility for ultra-thick electrodes in high-energy LMBs.
• • The integrated ionic-electronic scaffold couples fast Li+ conduction from NASICON core with electron transport via carbon shell, addressing tortuous transport pathways that typically limit dry-processed thick electrodes.
• • Pouch cells with 60 mg cm−2 LATP@C cathodes retain 80.5% capacity after 50 cycles, validating scalability and practical viability beyond coin-cell level.
• • Mechanically robust fibrous network bridges NCM811 secondary particles, suppressing crack initiation and preserving structural integrity under cycling-induced stress, which is critical for long-term cycling stability.