AgPF6 modified lithium interphases enable superior performance for Li5.5PS4.5Cl1.5-based all-solid-state lithium metal batteries.

All-solid-state lithium metal batteries (ASSLMBs) hold tremendous promise as next-generation energy storage devices due to their remarkable energy densities. Nevertheless, uncontrolled growth of lithium dendrites resulting from nonuniform deposition and significant volume expansion hinders the commercial application of ASSLMBs. Herein, we designed an AgPF 6 modified lithium composite anode to stabilize the interface between the lithium metal anode and Li 5.5 PS 4.5 Cl 1.5 electrolytes. The optimal AgPF 6 modified lithium composite accelerates Li diffusion within bulk lithium anode and facilitates the uniform deposition for lithium metal during the electrochemical process due to the generation of LiF-interface and Li–Ag alloy, which restricts the accumulation of inactive lithium. The enhanced compatibility between Li metal and sulfide electrolyte have been confirmed in both symmetric cells and ASSLMBs. The assembled AgPF 6 @Li/Li 5.5 AgPS 4.5 Cl 1.5 /AgPF 6 @Li cells shows a high critical current density value of 2.1 mA cm−2 and a stable lithium stripping/platting behavior up to 400 h at 0.1 mA cm−2. The LiNi 0.6 Mn 0.2 Co 0.2 O 2 /Li 5.5 PS 4.5 Cl 1.5 /AgPF 6 @Li battery delivers an initial discharge capacity of 113.5 mAh g−1 at 0.5C with superior capacity retention of 77.0% after 500 cycles at room temperature. This work proposes an effective strategy in designing composite lithium metal employing in sulfide-based ASSLMBs to achieve favorable energy density and excellent cyclability. The kinetic instability between lithium and sulfide electrolyte hinders the practical feasibility of all-solid-state batteries. A homogeneous Li–F–Ag composite lithium anode is formed via the conversion reaction, the optimal Ag–F modified lithium composite accelerates Li+ diffusion and facilitates the uniform deposition of lithium metal during the electrochemical process due to the generation of LiF-interface and Li–Ag alloy, which restricts the accumulation of inactive lithium. [Display omitted] • AgPF 6 modification strategy on the lithium metal exhibits enhanced compatibility with the Li 5.5 PS 4.5 Cl 1.5 electrolytes. • The assembled NCM622/Li 5.5 PS 4.5 Cl 1.5 /AgPF 6 @Li all-solid-state lithium metal battery delivers a high initial discharge capacity of 113.5 mAh g−1 at 0.5C and maintains 77% of its original capacity after 500 cycles. • The optimal Ag–F modified lithium composite accelerates Li+ diffusion and facilitates the uniform deposition of lithium metal during the electrochemical process dur to the generation of LiF-interface and Li–Ag alloy. [ABSTRACT FROM AUTHOR]