ABSTRACT Li metal batteries (LMBs) offer high energy density but suffer from Li dendrite growth and unstable solid–electrolyte interphase (SEI). Beyond conventional liquid systems, nanocolloid electrolytes (NCEs) incorporating insoluble nanoparticles dispersed in liquid electrolytes have emerged to mediate Li + solvation and SEI formation, which are key factors governing Li dendrite suppression. Nonetheless, their practical application has been limited by an intrinsic trade‐off between nanoparticle surface area and colloidal stability. To address this limitation, we propose an intrapore‐structuring strategy that enables facile Li + transport and efficient SEI regulation. Incorporating well‐ordered mesopores into SiO 2 nanobeads achieves high surface area while retaining dispersibility by alleviating interparticle attraction. The intrapore‐structured NCE alleviates viscosity increase, enhances anion mediation at the interface, and thereby effectively suppresses Li dendrite growth while promoting the buildup of anion‐derived SEI. The LMB employing the intrapore‐structured NCE demonstrates cycling stability over 300 cycles at 70% capacity retention and fast‐charging capability up to 3 C, far outperforming NCEs using nonporous nanobeads and 7 nm‐sized nanoparticles. This work establishes intrapore‐structuring as a new design principle for realizing the practical potential of NCEs in LMBs.
Lee et al. (Wed,) studied this question.