Pulverisette 7pl

To prepare ZrO₂(-ACl)-A₂ZrCl₆ (A = Li or Na), a stoichiometric mixture of Li₂O (99.5%, Alfa Aesar) or Na₂O (80%, Sigma Aldrich, ~20% Na₂O₂), LiCl (99.99%, Sigma Aldrich) or NaCl (99.99%, Alfa Aesar), and ZrCl₄ (99.99%, Sigma Aldrich) was ball-milled at 600 rpm for 20 h in a ZrO₂ vial with ZrO₂ balls using Pulverisette 7PL (Fritsch GmbH) under Ar atmosphere. To prepare fluorinated HNSE ZrO₂-2Li₂ZrCl₅F, a stoichiometric mixture (Li₂O: ZrF₄: ZrCl₄ = 2: 0.5: 2.5) of Li₂O (99.5%, Alfa Aesar), ZrF₄ (99.9%, Sigma Aldrich) and ZrCl₄ (99.99%, Sigma Aldrich) was ball-milled under the same condition as for the conventional HNSEs. To prepare nM_yO_z-Li₂ZrCl₆ nanomixtures, M_yO_z nanoparticles were ball-milled at 600 rpm for 20 h in a ZrO₂ vial with ZrO₂ balls using Pulverisette 7PL (Fritsch GmbH). ZrO₂ (99.95%, 20 nm) and Al₂O₃ (≥95%, 50 nm) nanopowders were purchased from Avention and Sigma Aldrich, respectively. Fumed SiO₂ powders were obtained from Sigma Aldrich. For the preparation of Li₆PS₅Cl, a stoichiometric mixture of Li₂S (99.9%, Alfa Aesar), P₂S₅ (99%, Sigma Aldrich), and LiCl (99.99%, Sigma Aldrich) was ball-milled at 600 rpm for 10 h in a ZrO₂ vial with ZrO₂ balls, followed by annealing at 550 °C for 6 h under an Ar atmosphere.

The amorphous SSEs of binary xLi₂S-(100-x)LiI (x = 10, 30, 50, 70, 90) were synthesized through a ball milling process. First, the starting materials of Li₂S (Alfa Aesar, 99.9%) and LiI (Energy chemical, 98%) were ground in an agate mortar for 30 min to get the homogeneous mixture. Then, the stoichiometric mixtures of Li₂S and LiI were ball-milled at 500 rpm for 33 h in a grinding jar with ZrO₂ balls using planetary ball mill (Pulverisette 7 PL, Fritsch). The ball-to-powder mass ratio is 20:1 during sample preparation, and each cycle running for 15 min and resting for 5 min. The entire preparation process were carried out under an argon atmosphere (O₂ < 0.1 ppm, H₂O < 0.1 ppm).