A thermodynamic approach at the nanometer scale was performed for the heterogeneous nucleation inside nanocavity, and an analytical expression of the critical energy of nucleation was evaluated considering a rough bal...A thermodynamic approach at the nanometer scale was performed for the heterogeneous nucleation inside nanocavity, and an analytical expression of the critical energy of nucleation was evaluated considering a rough ball nucleus nucleating inside nanocavity. Compared with the case of the nucleation locating on planar or convex substrate, the critical energy of nucleation inside the concave substrate is the smallest. Based on the thermodynamic and kinetic analyses, at low supersaturation, the smaller the curvature radius of cavity and/or the smaller the contact angle, the smaller the critical energy of nucleation, and the larger the nucleation rate. At high supersaturation, the nucleation rate increases with increasing the contact angle and/or increasing the curvature radius of cavity. In this way, at the low supersaturation, the heterogeneous nucleation rate is larger than the homogeneous one, as the nucleation rate is mainly determined by the heterogeneous nucleation. At the high supersaturation, the heterogeneous nucleation rate is smaller than the homogeneous one, as the nucleation rate is mainly determined by the homogeneous nucleation.展开更多
Lithium metal has gained extensive attention as the most ideal candidate for next-generation battery anode owing to the ultrahigh specific capacity and the lowest electrochemical potential.However,uncontrollable dendr...Lithium metal has gained extensive attention as the most ideal candidate for next-generation battery anode owing to the ultrahigh specific capacity and the lowest electrochemical potential.However,uncontrollable dendrite growth and huge volume variation extremely restrict the future deployment of lithium metal batteries.Herein,we report metal chalcogenide SnSSe with unique nanoplate stacking structure as a robust substrate for stable Li metal anode.During the initial Li plating process,lithiophilic Li_(22)Sn_(5) alloy and Li_(2)S/Li_(2)Se sites are obtained via in-situ electrochemical reaction of Li metal and SnSSe.Density functional theory(DFT)calculation demonstrates that the formed Li_(2)S/Li_(2)Se achieves low Li diffusion energy barrier,ensuring rapid Li~+migration.Li_(22)Sn_(5) alloy provides strong nucleation sites,promoting uniform Li nucleation.Furthermore,in-situ optical microscopy analysis suggests that the synthesized effect fundamentally inhibits lithium dendrite growth.Consequently,SnSSe modified Cu foil delivered an ultralow nucleation overpotential,superior cycling stability with 450 cycles(Coulombic efficiency,>98%),and excellent plating/stripping behavior over 2200 h at 0.5 mA cm^(-2).Moreover,the brilliant reversible cycles and rate capability were also realized in Li@SnSSe//LiFePO_(4)(LFP)full cell,shedding light on the feasibility of SnSSe for stable and dendrite-free lithium metal anode.展开更多
基金supported by the Natural Science Foundation of Guangdong Province under Grant Nos.04300168 and 04009487Doctor Fund of Guangdong University of Technology.
文摘A thermodynamic approach at the nanometer scale was performed for the heterogeneous nucleation inside nanocavity, and an analytical expression of the critical energy of nucleation was evaluated considering a rough ball nucleus nucleating inside nanocavity. Compared with the case of the nucleation locating on planar or convex substrate, the critical energy of nucleation inside the concave substrate is the smallest. Based on the thermodynamic and kinetic analyses, at low supersaturation, the smaller the curvature radius of cavity and/or the smaller the contact angle, the smaller the critical energy of nucleation, and the larger the nucleation rate. At high supersaturation, the nucleation rate increases with increasing the contact angle and/or increasing the curvature radius of cavity. In this way, at the low supersaturation, the heterogeneous nucleation rate is larger than the homogeneous one, as the nucleation rate is mainly determined by the heterogeneous nucleation. At the high supersaturation, the heterogeneous nucleation rate is smaller than the homogeneous one, as the nucleation rate is mainly determined by the homogeneous nucleation.
基金financially supported by the National Natural Science Foundation of China(52074113,22005091,and 22005092)the Hunan University Outstanding Youth Science Foundation(531118040319)+5 种基金the Science and Technology Innovation Program of Hunan Province(2021RC3055)the Changsha Municipal Natural Science Foundation(kq2014037)the CITIC Metals Ningbo Energy Co.Ltd.(H202191380246)the Chongqing Talents:Exceptional Young Talents Project(CQYC202105015)the Shenzhen Virtual University Park Basic Research Project of Free exploration(2021Szvup036)financially supported by the Graduate Research and Innovation Projects of Hunan Province(QL20210088)。
文摘Lithium metal has gained extensive attention as the most ideal candidate for next-generation battery anode owing to the ultrahigh specific capacity and the lowest electrochemical potential.However,uncontrollable dendrite growth and huge volume variation extremely restrict the future deployment of lithium metal batteries.Herein,we report metal chalcogenide SnSSe with unique nanoplate stacking structure as a robust substrate for stable Li metal anode.During the initial Li plating process,lithiophilic Li_(22)Sn_(5) alloy and Li_(2)S/Li_(2)Se sites are obtained via in-situ electrochemical reaction of Li metal and SnSSe.Density functional theory(DFT)calculation demonstrates that the formed Li_(2)S/Li_(2)Se achieves low Li diffusion energy barrier,ensuring rapid Li~+migration.Li_(22)Sn_(5) alloy provides strong nucleation sites,promoting uniform Li nucleation.Furthermore,in-situ optical microscopy analysis suggests that the synthesized effect fundamentally inhibits lithium dendrite growth.Consequently,SnSSe modified Cu foil delivered an ultralow nucleation overpotential,superior cycling stability with 450 cycles(Coulombic efficiency,>98%),and excellent plating/stripping behavior over 2200 h at 0.5 mA cm^(-2).Moreover,the brilliant reversible cycles and rate capability were also realized in Li@SnSSe//LiFePO_(4)(LFP)full cell,shedding light on the feasibility of SnSSe for stable and dendrite-free lithium metal anode.