Chlorine-rich argyrodite electrolytes,despite their exceptional ionic conductivity,face critical challenges in industrial utilization of all-solid-state lithium batteries(ASSLBs)due to inherent air instability and uns...Chlorine-rich argyrodite electrolytes,despite their exceptional ionic conductivity,face critical challenges in industrial utilization of all-solid-state lithium batteries(ASSLBs)due to inherent air instability and unsatisfactory compatibility with lithium metal anodes.To solve this problem,this work doped the P unit in Li_(5.5)PS_(4.5)Cl_(1.5),yielding a modified electrolyte LPSC-5%Li_(3)PO_(4)with significantly enhanced chemical/electrochemical stability.The integration of P units within the bulk structure reinforces lattice stability through robust P-O bonding while inhibiting reactive sulfur species responsible for moisture-triggered H_(2)S generation,resulting in enhanced air/moisture stability.Moreover,the electrolyte demonstrates an ionic conductivity of 5.71 mS cm^(-1)coupled with an exceptional critical current density reaching 2.9 mA cm^(-2),indicating robust dendrite suppression capability.Notably,the P-doped into the LPSC electrolyte induces multifaceted interfacial enhancements:a composite interphase layer consisting of LiCl and Li_(3)OCl phases is spontaneously formed at the lithium/electrolyte interface.Physical field simulations demonstrate that the electrolyte exhibits excellent mechanical stability,effectively suppressing the penetration of lithium dendrites.Chemically,Density functional theory calculations reveal that the electrolyte possesses a high lowest unoccupied molecular orbital potential,demonstrating good compatibility with lithium metal.This multifaced mechanism synergistically inhibits dendritic lithium growth by simultaneously passivating reactive interfaces and homogenizing ion transport dynamics.The assembled ASSLBS enables stable cycling performance,delivering an initial discharge capacity of 146.7 mAh g^(-1)and a capacity retention of 80.0%after 1000 cycles at 0.5 C.This work establishes a straightforward and effective doping paradigm that simultaneously addresses ionic transport efficiency,air stability,and interfacial compatibility in sulfide-based electrolytes.The proposed strategy provides critical insights into the rational design of high-energy-density ASSLBs with superior cyclability.展开更多
Sulfide-based all-solid-state lithium metal batteries(ASSLMBs)have received extensive attention due to their high energy density and high safety,while the poor interface stability between sulfide electrolyte and lithi...Sulfide-based all-solid-state lithium metal batteries(ASSLMBs)have received extensive attention due to their high energy density and high safety,while the poor interface stability between sulfide electrolyte and lithium metal anode limits their development.Hence,a hybrid SEI(LICl/Li F/Li Zn)was constructed at the interface between Li_(5.5)PS_(4.5)Cl_(1.5)sulfide electrolyte and lithium metal.The Li Cl and Li F interface phases with high interface energy effectively induce the uniform deposition of Li^(+)and reduce the overpotential of Li^(+)deposition,while the Li Zn alloy interface phase accelerates the diffusion of lithium ions.The synergistic effect of the above functional interface phases inhibits the growth of lithium dendrites and stabilizes the interface between the sulfide electrolyte and lithium metal.The hybrid SEI strategy exhibits excellent electrochemical performance on symmetric batteries and all-solid-state batteries.The symmetrical cell exhibits stable cycling performance over long duration over 500 h at 1.0 mA cm^(-2).Moreover,the LiNbO_(3)@NCM712/Li_(5.5)PS_(4.5)Cl_(1.5)/Li-10%Zn F_(2)battery exhibits excellent cycle stability at a high rate of 0.5 C,with a capacity retention rate of 76.4%after 350 cycles.展开更多
基金supported by the National Key Research and Development Program of China(2021YFB2500200)the National Natural Science Foundation of China(52177214)+1 种基金the Basic Science Research Fund in Xidian University(ZYTS24132)the Postdoctoral Science Research Program of Shaanxi(30102230001)。
文摘Chlorine-rich argyrodite electrolytes,despite their exceptional ionic conductivity,face critical challenges in industrial utilization of all-solid-state lithium batteries(ASSLBs)due to inherent air instability and unsatisfactory compatibility with lithium metal anodes.To solve this problem,this work doped the P unit in Li_(5.5)PS_(4.5)Cl_(1.5),yielding a modified electrolyte LPSC-5%Li_(3)PO_(4)with significantly enhanced chemical/electrochemical stability.The integration of P units within the bulk structure reinforces lattice stability through robust P-O bonding while inhibiting reactive sulfur species responsible for moisture-triggered H_(2)S generation,resulting in enhanced air/moisture stability.Moreover,the electrolyte demonstrates an ionic conductivity of 5.71 mS cm^(-1)coupled with an exceptional critical current density reaching 2.9 mA cm^(-2),indicating robust dendrite suppression capability.Notably,the P-doped into the LPSC electrolyte induces multifaceted interfacial enhancements:a composite interphase layer consisting of LiCl and Li_(3)OCl phases is spontaneously formed at the lithium/electrolyte interface.Physical field simulations demonstrate that the electrolyte exhibits excellent mechanical stability,effectively suppressing the penetration of lithium dendrites.Chemically,Density functional theory calculations reveal that the electrolyte possesses a high lowest unoccupied molecular orbital potential,demonstrating good compatibility with lithium metal.This multifaced mechanism synergistically inhibits dendritic lithium growth by simultaneously passivating reactive interfaces and homogenizing ion transport dynamics.The assembled ASSLBS enables stable cycling performance,delivering an initial discharge capacity of 146.7 mAh g^(-1)and a capacity retention of 80.0%after 1000 cycles at 0.5 C.This work establishes a straightforward and effective doping paradigm that simultaneously addresses ionic transport efficiency,air stability,and interfacial compatibility in sulfide-based electrolytes.The proposed strategy provides critical insights into the rational design of high-energy-density ASSLBs with superior cyclability.
基金supported by the National Key Research and Development Program of China(2021YFB2500200)the National Natural Science Foundation of China(52177214)+1 种基金supported by China Fujian Energy Devices Science and Technology Innovation Laboratory Open Fund(21C-OP202211)HUST’s Analytical and Testing Center for the technical support。
文摘Sulfide-based all-solid-state lithium metal batteries(ASSLMBs)have received extensive attention due to their high energy density and high safety,while the poor interface stability between sulfide electrolyte and lithium metal anode limits their development.Hence,a hybrid SEI(LICl/Li F/Li Zn)was constructed at the interface between Li_(5.5)PS_(4.5)Cl_(1.5)sulfide electrolyte and lithium metal.The Li Cl and Li F interface phases with high interface energy effectively induce the uniform deposition of Li^(+)and reduce the overpotential of Li^(+)deposition,while the Li Zn alloy interface phase accelerates the diffusion of lithium ions.The synergistic effect of the above functional interface phases inhibits the growth of lithium dendrites and stabilizes the interface between the sulfide electrolyte and lithium metal.The hybrid SEI strategy exhibits excellent electrochemical performance on symmetric batteries and all-solid-state batteries.The symmetrical cell exhibits stable cycling performance over long duration over 500 h at 1.0 mA cm^(-2).Moreover,the LiNbO_(3)@NCM712/Li_(5.5)PS_(4.5)Cl_(1.5)/Li-10%Zn F_(2)battery exhibits excellent cycle stability at a high rate of 0.5 C,with a capacity retention rate of 76.4%after 350 cycles.
