Interface Analysis of LiCl as a Protective Layer of Li_1.3Al_0.3Ti_1.7(PO₄)₃ for Electrochemically Stabilized All-Solid-State Li-Metal Batteries

Abstract

Regardless of the superiorities of Li1.3Al0.3Ti1.7(PO4)3 (LATP), such as stability against oxygen and moisture, high ionic conductivity, and low activation energy, its practical application in all-solid-state lithium metal batteries is still impeded by the formation of ionic-resistance interphase layers. Upon contact with Li metal, electron migration from Li to LATP causes the reduction of Ti4+ in LATP. As a result, an ionic-resistance layer will be formed at the interface between the two materials. Applying a buffer layer between them is a potential measure to mitigate this problem. In this study, we analyzed the potential role of LiCl to protect the LATP solid electrolyte through a first-principle study-based density functional theory (DFT) calculation. Density-of-states (DOS) analysis on the Li/LiCl heterostructure reveals the insulating roles of LiCl in preventing electron flow to LATP. The insulating properties begin at depths of 4.3 and 5.0 Å for Li (001)/LiCl (111) and Li (001)/LiCl (001) heterostructures, respectively. These results indicate that LiCl (111) is highly potential to be applied as a protecting layer on LATP to avoid the formation of ionic resistance interphase caused by electron transfer from the Li metal anode.

Novel strategy for high-performance supercapacitors through the polyvinylpyrrolidone (PVP)-assisted in situ growth of FeS2

“…S6 †). 64 From the charge-difference analysis in Fig. 4d, it could be confirmed that the PVP not only hybridized with the FeS 2 surface but also changed the charge symmetricity of the FeS 2 surface.…”

Low-Temperature In Situ Lithiation Construction of a Lithiophilic Particle-Selective Interlayer for Solid-State Lithium Metal Batteries

“…LiCl has been confirmed that it could work as an interfacial buffer layer hindering the injection of electrons from the lithium anode to the solid electrolyte due to its excellent electronic insulation properties via a first-principles study. 47 Therefore, a 3D cross-linked structure was generated during in situ lithiation in which a large number of nanoscale SbLi 3 alloy particles embedded in the electronically insulating LiCl matrix.…”

“…46 Moreover, the electronic insulator LiCl matrix with better lithiophilicity than garnet-type solid electrolytes enables the suppression of electron injection into the solid-state electrolyte and the formation of diffuse lithium dendrites. 47 With the assistance of LM-like SbCl 3 , the area-specific resistance (ASR) of Li/Li symmetric cells is reduced to 6 Ω cm −2 and the CCD is increased to 6.0 mA cm −2 at room temperature. The Li/Li symmetric cells can stably work for over 1000 h at a current density of 2.0 mA cm −2 with an extremely low overpotential and no significant interface failure.…”

“…Meanwhile, the generated SbLi 3 is favorable for Li + transfer across the interface with a low migration barrier . Moreover, the electronic insulator LiCl matrix with better lithiophilicity than garnet-type solid electrolytes enables the suppression of electron injection into the solid-state electrolyte and the formation of diffuse lithium dendrites . With the assistance of LM-like SbCl 3 , the area-specific resistance (ASR) of Li/Li symmetric cells is reduced to 6 Ω cm –2 and the CCD is increased to 6.0 mA cm –2 at room temperature.…”

Synthesis and Sintering of Li1.3Al0.3Ti1.7(PO4)3@Li2O–2B2O3 Core–Shell Solid Electrolyte Powders Prepared via One‐Pot Spray Pyrolysis

“…[ 44 ] In addition to the limitation of high sintering temperature, NASICON‐type solid electrolytes undergo side reactions with Li metal. [ 45–50 ] Consequently, numerous studies have been conducted to ensure stability at the interface between Li metal and solid electrolytes. Yang et al suppressed the chemical reaction between LATP and Li by interposing a poly(ethylene oxide) thin film between LATP and Li metal.…”