Tailoring Conversion‐Reaction‐Induced Alloy Interlayer for Dendrite‐Free Sulfide‐Based All‐Solid‐State Lithium‐Metal Battery

Abstract

Utilization of lithium (Li) metal anodes in all‐solid‐state batteries employing sulfide solid electrolytes is hindered by diffusion‐related dendrite growth at high rates of charge. Engineering ex‐situ Li‐intermetallic interlayers derived from a facile solution‐based conversion‐alloy reaction is attractive for bypassing the Li0 self‐diffusion restriction. However, no correlation is established between the properties of conversion‐reaction‐induced (CRI) interlayers and the deposition behavior of Li0 in all‐solid‐state lithium‐metal batteries (ASSLBs). Herein, using a control set of electrochemical characterization experiments with LixAgy as the interlayer in different battery chemistries, this work identifies that dendritic tolerance in ASSLBs is susceptible to the surface roughness and electronic conductivity of the CRI‐alloy interlayer. This work thereby tailors the CRI‐alloy interlayer from the typical mosaic structure to a hierarchical gradient structure by adjusting the pit corrosion kinetics from the (de)solvation mechanism to an adsorption model, yielding a smooth organic‐rich outer layer and a composition‐regulated inorganic‐rich inner layer composed mainly of lithiophilic LixAgy and electron‐insulating LiF. Ultimately, desirable roughness, conductivity, and diffusivity are integrated simultaneously into the tailored CRI‐alloy interlayer, resulting in dendrite‐free and dense Li deposition beneath the interlayer capable of improving battery cycling stability. This work provides a rational protocol for the CRI‐alloy interlayer specialized for ASSLBs.

Toward Ultrastable Metal Anode/Li6PS5Cl Interface via an Interlayer as Li Reservoir

“…According to the analysis details for Figure S12, it is concluded that, in all-solid-state batteries, the Pre In anode has the ability of improving interfacial compatibility and effective utilization of active Li, which is inseparable from the multifunctional interlayer formed on it. In comparison to other reports, ,,,− sulfide-based solid-state cells in this work show superior performances in view of the cycling life span, capacity retention, and areal current density (Figure e), which proves the effectiveness of a generated interlayer on the improvement of metal anode/LPSCl interface stability.…”

“…Further, resistance evolution of the anode interface was studied by employing in situ impedance coupled with distribution of relaxation times (DRT) spectra. With the assistance of electron-insulating LiF as a protective substance, − the interlayer can effectively inhibit the destruction of LPSCl and ensure low interface resistance. The application of the Pre In anode is also evaluated in an all-solid-state cell.…”

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

“…The Ag-decorated Li anode was prepared by pretreating the Li foil with AgNO 3 (0.05 M) dissolved in DME-NMP (9:1) for 30 min. The Ag-decoration could greatly improve the lithium puncture resistance. , The PEO-LLZTO (EO/Li = 15, 10 wt %) separator was prepared by the casting method, whose thickness was 80 μm . To prevent the cathode active materials dissolving into PEO that induces the noxious “polysulfide shuttling” effect, a thin layer of Li 3 PS 4 was sprayed on the top of the Li 2 S cathode with the Li 3 PS 4 precursor sol and sintered together with the cathode.…”