Lithium metal anode holds an important position in fast-charging batteries.But lithium dendrite issues tend to exacerbate at high currents.Li F can be considered as an effective way to improve the Li metal surface ele...Lithium metal anode holds an important position in fast-charging batteries.But lithium dendrite issues tend to exacerbate at high currents.Li F can be considered as an effective way to improve the Li metal surface electrochemical stability to achieve high power and high energy.However,most of reported work are relying on in situ formation of a 2D Li F on Li metal in liquid electrolyte,which limits the scalability and plated Li quantity.Here,we address this challenge and report a scalable synthesis of Li F-rich 3D architected Li metal anode via a direct pyrolysis of molten lithium and fluoropolymer to enable fast Li charging with high current density(20 mA cm-2)and high areal capacity(20 m Ah cm-2).The 3D structure is synthesized by the pyrolysis of fluoropolymer with Li metal and results show high similarity to the pristine electrolyte-derived solid-electrolyte-interphase(SEI).This concept using pyrolysis of fluoropolymer with Li-containing active materials could be also extended to modify Li metal oxide cathode(e.g.,Li Ni0.5Mn1.5O4)for mixed conductive interphase and engineer Li solid ion conductors(e.g.,Li garnet-type oxides)for interface stabilization andframework design.展开更多
Sulfide-based solid-state electrolytes(SSEs)with high Li+conductivity(δLi^(+))and trifling grain boundaries have great potential for all-solid-state lithium-metal batteries(ASSLMBs).Nonetheless,the in-situ developmen...Sulfide-based solid-state electrolytes(SSEs)with high Li+conductivity(δLi^(+))and trifling grain boundaries have great potential for all-solid-state lithium-metal batteries(ASSLMBs).Nonetheless,the in-situ development of mixed ionic-electronic conducting solid-electrolyte interphase(SEI)at sulfide electrolyte/Li-metal anode interface induces uneven Li electrodeposition,which causes Li-dendrites and void formation,significantly severely deteriorating ASSLMBs.Herein,we propose a dual anionic,e.g.,F and N,doping strategy to Li7P3S11,tuning its composition in conjunction with the chemistry of SEI.Therefore,novel Li_(6.58)P_(2.76)N_(0.03)S_(10.12)F_(0.05)glass-ceramic electrolyte(Li_(7)P_(3)S_(11-5)LiF-3Li_(3)N-gce)achieved superior ionic(4.33 mS·cm^(−1))and lowest electronic conductivity of 4.33×10^(−10)S·cm^(−1)and thus,offered superior critical current density of 0.90 mA·cm^(−2)(2.5 times】Li7P3S11)at room temperature(RT).Notably,Li//Li cell with Li6.58P2.76N0.03S10.12F0.05-gce cycled stably over 1000 and 600 h at 0.2 and 0.3 mA·cm^(−2)credited to robust and highly conductive SEI(in-situ)enriched with LiF and Li3N species.Li3N’s wettability renders SEI to be highly Li+conductive,ensures an intimate interfacial contact,blocks reductive reactions,prevents Li-dendrites and facilitates fast Li+kinetics.Consequently,LiNi0.8Co0.15Al0.05O_(2)(NCA)/Li_(6.58)P_(2.76)N_(0.03)S_(10.12)F_(0.05)-gce/Li cell exhibited an outstanding first reversible capacity of 200.8/240.1 mAh·g^(−1)with 83.67%Coulombic efficiency,retained 85.11%of its original reversible capacity at 0.3 mA·cm^(−2)over 165 cycles at RT.展开更多
基金supported by the startup funding at University of Delaware
文摘Lithium metal anode holds an important position in fast-charging batteries.But lithium dendrite issues tend to exacerbate at high currents.Li F can be considered as an effective way to improve the Li metal surface electrochemical stability to achieve high power and high energy.However,most of reported work are relying on in situ formation of a 2D Li F on Li metal in liquid electrolyte,which limits the scalability and plated Li quantity.Here,we address this challenge and report a scalable synthesis of Li F-rich 3D architected Li metal anode via a direct pyrolysis of molten lithium and fluoropolymer to enable fast Li charging with high current density(20 mA cm-2)and high areal capacity(20 m Ah cm-2).The 3D structure is synthesized by the pyrolysis of fluoropolymer with Li metal and results show high similarity to the pristine electrolyte-derived solid-electrolyte-interphase(SEI).This concept using pyrolysis of fluoropolymer with Li-containing active materials could be also extended to modify Li metal oxide cathode(e.g.,Li Ni0.5Mn1.5O4)for mixed conductive interphase and engineer Li solid ion conductors(e.g.,Li garnet-type oxides)for interface stabilization andframework design.
基金The National Natural Science Foundation of China(Nos.21203008,21975025,12274025 and 22372008)Hainan Province Science and Technology Special Fund(Nos.ZDYF2021SHFZ232 and ZDYF2023GXJS022)Hainan Province Postdoctoral Science Foundation(No.300333)supported this work.
文摘Sulfide-based solid-state electrolytes(SSEs)with high Li+conductivity(δLi^(+))and trifling grain boundaries have great potential for all-solid-state lithium-metal batteries(ASSLMBs).Nonetheless,the in-situ development of mixed ionic-electronic conducting solid-electrolyte interphase(SEI)at sulfide electrolyte/Li-metal anode interface induces uneven Li electrodeposition,which causes Li-dendrites and void formation,significantly severely deteriorating ASSLMBs.Herein,we propose a dual anionic,e.g.,F and N,doping strategy to Li7P3S11,tuning its composition in conjunction with the chemistry of SEI.Therefore,novel Li_(6.58)P_(2.76)N_(0.03)S_(10.12)F_(0.05)glass-ceramic electrolyte(Li_(7)P_(3)S_(11-5)LiF-3Li_(3)N-gce)achieved superior ionic(4.33 mS·cm^(−1))and lowest electronic conductivity of 4.33×10^(−10)S·cm^(−1)and thus,offered superior critical current density of 0.90 mA·cm^(−2)(2.5 times】Li7P3S11)at room temperature(RT).Notably,Li//Li cell with Li6.58P2.76N0.03S10.12F0.05-gce cycled stably over 1000 and 600 h at 0.2 and 0.3 mA·cm^(−2)credited to robust and highly conductive SEI(in-situ)enriched with LiF and Li3N species.Li3N’s wettability renders SEI to be highly Li+conductive,ensures an intimate interfacial contact,blocks reductive reactions,prevents Li-dendrites and facilitates fast Li+kinetics.Consequently,LiNi0.8Co0.15Al0.05O_(2)(NCA)/Li_(6.58)P_(2.76)N_(0.03)S_(10.12)F_(0.05)-gce/Li cell exhibited an outstanding first reversible capacity of 200.8/240.1 mAh·g^(−1)with 83.67%Coulombic efficiency,retained 85.11%of its original reversible capacity at 0.3 mA·cm^(−2)over 165 cycles at RT.
