ABSTRACT Solid‐state electrolytes (SSEs) exhibit both high ionic conductivity and electrochemical stability, which are essential for next‐generation all‐solid‐state batteries (ASSBs). In this study, a high‐entropy strategy was employed to modify two distinct structural phases of Li 2 ZrCl 6 (LZC), resulting in a low‐crystallinity (lc‐) form of Li 1.92 (ZrHf) 0.25 (InTaNb) 0.16 Cl 6 and a high‐crystallinity (hc‐) form of Li 1.8 (ZrHfInTaNb) 0.2 Cl 6 . This approach overcomes the typical trade‐offs encountered in chloride‐based SSEs, achieving high ionic conductivities of 1.0 and 0.968 mS cm − 1 at 25°C, respectively, while maintaining an excellent oxidation potential exceeding 4.6 V (relative to Li + /Li). Furthermore, the lc phase benefits from an entropy‐driven amorphization process, resulting in an amorphous phase content of 72.77%. In contrast, the hc phase exhibits lattice contraction and the disappearance of atomic positions, thereby optimizing Li + migration. A full cell employing a Li‐In anode and sc‐NCM83 cathode demonstrated outstanding rate performance and long‐term stability, retaining over 80% capacity after 1600 cycles at 5C. This work validates the general applicability of the high‐entropy design in tuning the properties of SSEs across different crystalline states.
Wang et al. (Tue,) studied this question.