A Ceramic Network for Hybrid Solid Electrolyte Lithium Metal Batteries

ABSTRACT Hybrid solid electrolytes (HSEs) represent a promising material system for lithium metal batteries by combining high ionic conductive and mechanically strong inorganic with soft organic solid electrolytes. However, for HSEs consisting of ceramic fillers, lithium hopping between the polymer and ceramic phases remains unproven, emphasizing the tortuosity inside the polymer phase as a pivotal factor. Herein, we report an in‐plane aligned Li _6.6 La ₃ Zr _1.6 Ta _0.4 O ₁₂ (Ta‐LLZO) ceramic fiber network structure for HSEs and compare its morphological nature to typical LLZO‐based fillers. Simulations reveal a high tortuosity inside the polymer phase with a parallel to the electrodes aligned network structure, enabling dendritic structure blocking behavior, but still reaching decent ionic transport (0.44 mS cm ⁻¹ , 60°C). Post‐mortem microscopy analyses confirmed the dendrite blocking mechanism of the network, ultimately leading to long cycling lifetime of > 1100 h in symmetric lithium metal cells operated with 0.1 mA cm ⁻² at 60°C. Overall, the ceramic network HSE represents a superior morphology by combining decent ionic conductivity, low resistance and long cycling life in symmetric and full cells with LiFePO ₄ cathodes. The comparison of different filler characteristics with a special focus on tortuosity eventually facilitates the evaluation of these properties for the purpose of optimizing HSEs.