Surficial Sulfur Loss of Jet-Milled Li₆PS₅Cl Powder under Mild-Temperature Heat Treatment

Abstract

All-solid-state batteries employing inorganic solid electrolytes are considered a promising next-generation energy storage system. Especially, argyrodite-type Li 6 PS 5 Cl (LPSCl) was highlighted for its good ionic conductivity and malleability. In the electrode level, achieving an efficient Li + pathway even with the maximized active material proportion and electrode mass loading is vital for a high energy density. Therefore, a smaller solid electrolyte particle is highly sought for. Herein, we demonstrated a spiral jet mill process for refining LPSCl particle size. The mean particle size (D 50 ) of LPSCl was reduced from 39.9 to 1.9 μm where the ionic conductivity was decreased from 2.0 to 0.23 mS cm −1 . The postannealing in a mild-temperature range (T < 250 °C) led to the even more decreased ionic conductivity. Although the ionic conductivity was restored when T > 300 °C, this high-temperature annealing resulted in severe particle agglomeration. Spectroscopic observations revealed that particle surfaces were damaged during pulverization and irreversible sulfur losses occurred during the mild-temperature annealing.

Ultrathin Superhydrophobic Coatings for Air‐Stable Inorganic Solid Electrolytes: Toward Dry Room Application for All‐Solid‐State Batteries

“…Similar types were observed in the coated samples after HT (Figure S7, Supporting Information), possibly due to surface sulfur loss and/or reaction with traces of oxygen. [52] The weight fractions of the coating layers for P-LPSCl and FP-LPSCl were determined using thermogravimetric analysis (TGA) measurements to be 1-2 wt.% (Figure S8, Supporting Information).…”

Anion Engineering for Stabilizing Li Interstitial Sites in Halide Solid Electrolytes for All-Solid-State Li Batteries

“…Thus, this aspect would not be critical once the particles are well-micronized . In addition, this slight brittleness can mitigate the difficulties in the micronization processes. , …”

“…38 In addition, this slight brittleness can mitigate the difficulties in the micronization processes. 37,39 We further tested the dry-air stability, which is vital for cell fabrication (Figure 6). It is noteworthy that the high oxygen affinity of Zr-based halide SEs was pointed out by Nazar et al 40 For the dry-air stability test, LZC, LZCO-0.35, LZCO-0.55, and Li 2.5 Y 0.5 Zr 0.5 Cl 6 (LYZC) powders were stored in a dry room for 24 h. The LYZC powder was prepared according to the literature.…”

Dimensional Strategies for Bridging the Research Gap between Lab‐Scale and Potentially Practical All‐Solid‐State Batteries: The Role of Sulfide Solid Electrolyte Films

“…Synthetic techniques such as liquid-phase synthesis, wet-milling, and jet-milling have been used to achieve these advancements. [16,48,49,68,[98][99][100][101][102][103] The chemical instability of SSEs toward air and solvents is a critical factor that affects the processability and electrochemical stability of SSE films; [42,58,59,104] this is discussed later. It is crucial to note that most SSEs react with polar solvents, resulting in irreversible side reactions.…”

“…[139,145] The successful fabrication of SSE films with low thicknesses (<30 μm) and high uniformity depends on the choice of fabrication method, as well as the average particle size, particle size distribution, and morphology of the SSEs. [99,100,106] Finer particles may be beneficial for achieving lower thickness and higher uniformity. However, it is necessary to strike a balance between ionic conductivity and particle size, as contact and/or grain boundary resistances between SSE particles increase with decreasing particle size.…”