High-voltage superionic and humidity-tolerant Li2.5Sc0.5Zr0.5Cl6 conductor for lithium batteries via preferred orientation

Toward Achieving a High Ionic Conducting Halide Solid Electrolyte through Low-Cost Metal (Zr and Fe) and F Substitution and Their Admirable Performance in All-Solid-State Batteries

“…From this, the electrochemical stability window can be obtained from the initial oxidation and reduction potential of the electrolyte, which is clearly shown in the histogram (Figure S13). According to that, the Li 3 YCl 6 electrolyte displayed a wider electrochemical stability window between 1.17 and 3.98 V, which was well correlated with the previous reports. , However, the Li 2.4 Y 0.4 Zr 0.6 Cl 6 electrolyte clearly shows the electrochemical stability window in the range of 2.2–3.82 V, which largely reduces the stability window compared to the Li 3 YCl 6 system, since the oxidation/reduction potential of Zr 4+ is ∼3.82 V/1.75 V in Li 2 ZrCl 6 electrolyte, which is lower/higher than that of Y 3+ (4.2 V/0.59 V) in Li 3 YCl 6 electrolyte ,, After F substitution, the Li 2.4 Y 0.4 Zr 0.6 Cl 5.85 F 0.15 electrolytes would moreover preserve the similar electrochemical stability window of 1.34–3.76 V of the Li 3 YCl 6 system. The F substitution revealed that it has a tendency to suppress the negative effect or reduction of Zr 4+ in the Li 2.4 Y 0.4 Zr 0.6 Cl 5.85 F 0.15 electrolytes.…”

Halide solid-state electrolytes for all-solid-state batteries: structural design, synthesis, environmental stability, interface optimization and challenges

“…109 The research of van der Maas et al on a series of Li 3−x In 1−x Zr x Cl 6 showed that the conductivity reached a maximum value of 2.02 mS cm −1 , when x = Similarly, introducing Zr 4+ or Hf 4+ into Li 3 ScCl 6 didn't change the monoclinic structure. 115,116 Zr 4+ /Hf 4+ was randomly located at the Sc 3+ 2a site, resulting in local structural distortion due to the difference in ion radii. The partially occupied Li2and Li3-centered octahedra expanded, while the fully occupied Li1-centered octahedra shrank.…”

“…Li 2.5 Sc 0.5 Zr 0.5 Cl 6 exhibited an ionic conductivity of up to 2.23 mS cm −1 , which was 3.28-fold higher than that of pristine Li 3 ScCl 6 . 115 Li 2 ZrCl 6 had a metastable trigonal structure and stable monoclinic structure, and the trivalent metal ions (In 3+ , Sc 3+ , and Fe 3+ ) exhibited different substitution effects on these two structures. All Li 2+x Zr 1−x In x Cl 6 (0 # x # 1.0) annealed at 260 °C aer ball milling were of monoclinic phase with a space group of C2/m, and doping In 3+ didn't change the crystal structure.…”

“…The doping strategy could improve the ionic conductivity of halide SSEs and enhance their moisture resistance. 38,115 Li 3 YCl 6 was unstable in air and easily changed to YCl 3 $6H 2 O and LiCl$H 2 O upon contact with moisture, which was irreversible and couldn't be recovered by vacuum heating. Aer doping through the In 3+ , hydration intermediates were formed when Li 3 Y 1−x In x Cl 6 was exposed to moist air, rather than separated phases (Fig.…”

Stable electrode/electrolyte interfaces regulated by dual-salt and localized high-concentration strategies for high-voltage lithium metal batteries

“…1–3 The electrolytes act as a bridge between cathodes and anodes and also play a crucial role in the battery system, which determines the battery's efficiency, safety, and overall performance. 4 Therefore, designing a functional electrolyte that can tolerate a high-voltage cathode (HVC) and stabilize a high-active Li-metal anode (LMA) is urgently desirable.…”