Garnet-type Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 (LLZTO), a promising solid-state electrolyte, is reported to exhibit lithiophobicity. Herein, it is demonstrated that the origin of the lithiophobicity is closely related to the surface compositions of both the lithium and LLZTO. Surface impurities with high melting points such as Li 2 O, Li 2 CO 3 , LiOH, or LiF inhibit the wettability between lithium metal and LLZTO, and the widely adopted compositing strategy may improve the wettability by merely breaking the surface impurity layers. A simple but effective "polishingand-spreading" strategy is proposed to remove the surface impurities and obtain clean Li/LLZTO interfaces. Thus, a tight and continuous Li/LLZTO interface with an interfacial resistance of 17.5 Ω cm 2 is achieved, which leads to stable cycling of the symmetric Li cells and a critical current density up to 2.8 mA cm -2 . This work provides a new perspective to understand the lithiophilicity of garnet-type electrolytes and contributes to designing robust Li/garnet interfaces.

The thermodynamically more stable lithium halide hydroxide, Li2OHCl, is experimentally easier to synthesize than Li3OCl. However, the protonated antiperovskite has the low ionic conductivity at room temperature due to the...

Designing solid electrolytes with high room temperature (RT) conductivity is essential for the development of the next generation of solid-state batteries. Beyond the static structural framework, interaction between cation mobility...

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The development of solid-state electrolytes (SSEs) with high lithium ionic conductivities is critical for the realization of all-solid-state Li-ion batteries. Crystal structure distortions, Li polyhedron volumes, and anion charges in SSEs are reported to affect the energy landscapes, and it is paramount to investigate their correlations. Our works uncover the cooperative effect of lithium site distortions, anion charges, and lattice volumes on Li-ion migration energy barrier in superionic conductors of LiMS2 (M = Sc, Ti, V, Cr, Mn, Fe, Co, and Ni) and Li2MO3 (M = Sc, Ti, V, Cr, Mn, Fe, Co, and Ni). Combined with the Least Absolute Shrinkage and Selection Operator analyses, the volume and Continuous symmetrical methods (CSMs) of Li tetrahedral (Tet) sites appear to have a larger effect on the manipulation of Ea for Li migration, compared to that of Li octahedral (Oct) sites, which is further confirmed by the results from the face-centered cubic (fcc) anion lattice model. For the Tet–Oct–Tet Li migration path, the CSM (the volume of Li site) has a negative (positive) correlation with Ea, while for the Oct–Tet–Oct Li migration paths, opposite correlations have been observed. The understanding of the correlation between site preference, anion charge, lattice volume, and structural distortion as well as the prediction model of Ea in terms of these three factors, namely, C–V–D model, could be useful for the design of solid-state electrolytes with lower activation energy.