One Stone, Three Birds: An Air and Interface Stable Argyrodite Solid Electrolyte with Multifunctional Nanoshells

Abstract

Li6PS5Cl (LPSC) solid electrolytes, based on Argyrodite, have shown potential for developing high energy density and safe all‐solid‐state lithium metal batteries. However, challenges such as interfacial reactions, uneven Li deposition, and air instability remain unresolved. To address these issues, a simple and effective approach is proposed to design and prepare a solid electrolyte with unique structural features: Li6PS4Cl0.75‐OF0.25 (LPSC‐OF0.25) with protective LiF@Li2O nanoshells and F and O‐rich internal units. The LPSC‐OF0.25 electrolyte exhibits high ionic conductivity and the capability of “killing three birds with one stone” by improving the moist air tolerance, as well as the interface compatibility between the anode or cathode and the solid electrolyte. The improved performance is attributed to the peculiar morphology and the self‐generating and self‐healing interface coupling capability. When coupled with bare LiCoO2, the LPSC‐OF0.25 electrolyte enables stable operation under high cutoff voltage (≈4.65 V vs Li/Li+), thick cathodes (25 mg cm−2), and large current density (800 cycles at 2 mA cm−2). This rationally designed solid electrolyte offers promising prospects for solid‐state batteries with high energy and power density for future long‐range electric vehicles and aircrafts.

Spray-Printed Flexible Li2S Cathode with Inorganic Ion-Conductive Binder Nano-Li3PS4

“…Here, we emphasize that the observed sintering phenomenon of solvated Li 3 PS 4 nanoparticles is called low-temperature sintering. This can be understood that oxide solid electrolytes usually sinter at more than 1000 °C, , and the sintering temperature of certain sulfide solid electrolytes, such as Li 6 PS 5 Cl, reaches 530 °C . In this study, the sintering of the Li 3 PS 4 nanoparticles is completed at a low temperature of 250 °C without any pressure.…”

“…This can be understood that oxide solid electrolytes usually sinter at more than 1000 °C, 28,29 and the sintering temperature of certain sulfide solid electrolytes, such as Li 6 PS 5 Cl, reaches 530 °C. 30 In this study, the sintering of the Li 3 PS 4 nanoparticles is completed at a low temperature of 250 °C without any pressure. As mentioned above, both high pressure and a sintering temperature around 300 °C are required to sinter the coarse powder of the Li 2 S−P 2 S 5 solid electrolyte.…”

Enhancing Ionic Conductivity and Electrochemical Stability of Li3PS4 via Zn, F Co-Doping for All-Solid-State Li–S Batteries

“…The Li-ion conductivity of the prepared electrolyte reaches a maximum value of 1.23 × 10 –3 S cm –1 at x = 0.04, which is 4 times higher than that of Li 3 PS 4 . Due to the introduction of aliovalent ions through doping, more Li-ion interstitial is produced inside the lattice, increasing the concentration of charge carriers, and thus improving the ionic conductivity. , Nevertheless, owing to the high electronegativity of F atoms, the binding effect on Li-ion conduction is enhanced with the increase of doping amount, resulting in a decrease in ionic conductivity . But doping of aliovalent ions Zn 2+ adds external elements to the lattice, which disturbs the lattice of the material and generates more new vacancies or interstitial sites, which is very favorable for ionic conduction in the material and in this way improves the overall conductivity of the electrolyte.…”

“…12,48 Nevertheless, owing to the high electronegativity of F atoms, the binding effect on Li-ion conduction is enhanced with the increase of doping amount, resulting in a decrease in ionic conductivity. 49 But doping of aliovalent ions Zn 2+ adds external elements to the lattice, which disturbs the lattice of the material and generates more new vacancies or interstitial sites, which is very favorable for ionic conduction in the material and in this way improves the overall conductivity of the electrolyte. Table S2 provides a comparison of the conductivities of the prepared electrolyte in this work with previously reported solid-state electrolytes at room temperature.…”

Li-argyrodite solid-state electrolytes with lithium compatibility and air stability for all-solid-state batteries

“…The binding energies of each element were consistent with those in other previously reported literature. 23,38,40,43,49,58,59 The extremely high compatibility of this ZrO 2 -doped electrolyte with lithium metal anodes can be attributed to several reasons. First, as shown in Fig.…”