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.
