Argyrodite-based solid-state lithium metal batteries exhibit significant potential as next-generation energy storage devices.However,their practical applications are constrained by the intrinsic poor stability of argy...Argyrodite-based solid-state lithium metal batteries exhibit significant potential as next-generation energy storage devices.However,their practical applications are constrained by the intrinsic poor stability of argyrodite towards Li metal and exposure to air/moisture.Therefore,an indium-involved modification strategy is employed to address these issues.The optimized doping yields a high Li-ion conductivity of 7.5 mS cm^(-1)for Li_(5.54)In_(0.02)PS_(4.47)O_(0.03)Cl_(1.5)electrolyte,accompanied by enhanced endurance against air/moisture and bare Li metal.It retains 92.0%of its original conductivity after exposure to air at a low dew point of-60℃in dry room.Additionally,a composite layer comprising Li-In alloy and Li F phases is generated on the surface of lithium metal anode via the reaction between InF_(3)and molten Li.This layer effectively mitigates Li dendrite growth by creating a physical barrier from the robust LiF phase,while the Li-In alloy induces uniform Li-ion deposition and accelerates Li transport dynamics across the interphase between the solid electrolyte/Li metal.Moreover,the In-doped electrolyte facilitates the in-situ generation of Li-In alloy within its voids,reducing local current density and further inhibiting lithium dendrite growth.Consequently,the combination of the Li_(5.54)In_(0.02)PS_(4.47)O_(0.03)Cl_(1.5)electrolyte and the InF_(3)@Li anode provides exceptional electrochemical performances in both symmetric cells and solid-state lithium metal batteries across different operating temperatures.Specifically,the LiNbO_(3)@LiNi_(0.7)Co_(0.2)Mn_(0.1)O_(2)/Li_(5.54)In_(0.02)PS_(4.47)O_(0.03)Cl_(1.5)/InF_(3)@Li cell delivers a high discharge capacity of 167.8 mAh g^(-1)at 0.5 C under 25℃and retains 80.0%of its initial value after 400 cycles.This work offers a viable strategy for designing functional interfaces with enhanced stability for sulfide-based solid-state lithium batteries.展开更多
基金supported by the National Key Research and Development Program (2021YFB2500200)the National Natural Science Foundation of China (52177214,52222703)+1 种基金The Basic Science Research Fund in Xidian University (ZYTS24132)the Postdoctoral Science Research Program of Shaanxi (30102230001)。
文摘Argyrodite-based solid-state lithium metal batteries exhibit significant potential as next-generation energy storage devices.However,their practical applications are constrained by the intrinsic poor stability of argyrodite towards Li metal and exposure to air/moisture.Therefore,an indium-involved modification strategy is employed to address these issues.The optimized doping yields a high Li-ion conductivity of 7.5 mS cm^(-1)for Li_(5.54)In_(0.02)PS_(4.47)O_(0.03)Cl_(1.5)electrolyte,accompanied by enhanced endurance against air/moisture and bare Li metal.It retains 92.0%of its original conductivity after exposure to air at a low dew point of-60℃in dry room.Additionally,a composite layer comprising Li-In alloy and Li F phases is generated on the surface of lithium metal anode via the reaction between InF_(3)and molten Li.This layer effectively mitigates Li dendrite growth by creating a physical barrier from the robust LiF phase,while the Li-In alloy induces uniform Li-ion deposition and accelerates Li transport dynamics across the interphase between the solid electrolyte/Li metal.Moreover,the In-doped electrolyte facilitates the in-situ generation of Li-In alloy within its voids,reducing local current density and further inhibiting lithium dendrite growth.Consequently,the combination of the Li_(5.54)In_(0.02)PS_(4.47)O_(0.03)Cl_(1.5)electrolyte and the InF_(3)@Li anode provides exceptional electrochemical performances in both symmetric cells and solid-state lithium metal batteries across different operating temperatures.Specifically,the LiNbO_(3)@LiNi_(0.7)Co_(0.2)Mn_(0.1)O_(2)/Li_(5.54)In_(0.02)PS_(4.47)O_(0.03)Cl_(1.5)/InF_(3)@Li cell delivers a high discharge capacity of 167.8 mAh g^(-1)at 0.5 C under 25℃and retains 80.0%of its initial value after 400 cycles.This work offers a viable strategy for designing functional interfaces with enhanced stability for sulfide-based solid-state lithium batteries.
