Nanostructured materials have received tremendous interest due to their unique mechanical/electrical properties and overall behavior contributed by the complex synergy of bulk and interfacial properties for efficient ...Nanostructured materials have received tremendous interest due to their unique mechanical/electrical properties and overall behavior contributed by the complex synergy of bulk and interfacial properties for efficient and effective energy conversion and storage. The booming development of nanotechnology affords emerging but effective tools in designing advanced energy material. We reviewed the significant progress and dominated nanostructured energy materials in electrochemical energy conversion and storage devices, including lithium ion batteries, lithium-sulfur batteries, lithium-oxygen batteries, lithium metal batteries, and supercapacitors. The use of nanostructured electrocatalyst for effective electrocatalysis in oxygen reduction and oxygen evolution reactions for fuel cells and metal-air batteries was also included. The challenges in the undesirable side reactions between electrolytes and electrode due to high electrode/electrolyte contact area, low volumetric energy density of electrode owing to low tap density, and uniform production of complex energy materials in working devices should be overcome to fully demonstrate the advanced energy nanostructures for electrochemical energy conversion and storage. The energy chemistry at the interfaces of nanostructured electrode/electrolyte is highly expected to guide the rational design and full demonstration of energy materials in a working device. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.展开更多
金属锂具有高理论比容量和低氧化还原电位,被认为是高能量密度二次电池最理想的负极材料之一,但其在循环过程中的枝晶生长和体积变化易造成电池失效和安全隐患.以孔径为 5 μm 左右的自制三维多孔铜为基底,在其表面电沉积锌层(3D Cu@Zn)...金属锂具有高理论比容量和低氧化还原电位,被认为是高能量密度二次电池最理想的负极材料之一,但其在循环过程中的枝晶生长和体积变化易造成电池失效和安全隐患.以孔径为 5 μm 左右的自制三维多孔铜为基底,在其表面电沉积锌层(3D Cu@Zn),作为金属锂沉积的集流体,构筑无枝晶锂金属电极.三维多孔铜的孔结构稳定,孔径大小适宜,可有效降低局部电流密度和缓解体积变化.锌镀层可降低锂金属的形核过电位,诱导锂的均匀沉积,有效抑制锂枝晶生长.以 3D Cu@Zn 为集流体,锂沉积面积容量为 4 m Ah·cm^(-2),电极表面仍无枝晶出现,经过锂剥离后表面仍然光滑;而铜箔上沉积的锂显示明显的枝晶和不均匀性,3D Cu 上沉积的锂显示局部不均匀性和一定量枝晶.在电流密度为 0.5 和 1m A·cm^(-2),面积容量为 1 m Ah·cm^(-2)条件下,Li||3D Cu@Zn 半电池获得了稳定的库伦效率;在 2 m A·cm^(-2)的高电流密度和 1 m Ah·cm^(-2)的面积容量条件下,Li||3D Cu@Zn@Li 对称电池可稳定循环 700 h 以上;以 3D Cu@Zn@Li 为负极,Li Fe PO_(4)为正极的全电池,在 1 C 倍率下,经过 150 次循环后仍保持 88 m Ah·g^(-1)的容量,均明显优于 Cu 片和 3D Cu 作为集流体的锂金属电极.展开更多
金属锂因其具有极高的理论容量(3860 mAh·g^(−1))、最低的电极电位(−3.04 V vs.标准氢电极)和低的密度(0.534 g·cm^(−3)),被认为是最具潜力的负极材料。但循环过程中不可控的枝晶生长及不稳定的固体电解质相界面膜所引起的安...金属锂因其具有极高的理论容量(3860 mAh·g^(−1))、最低的电极电位(−3.04 V vs.标准氢电极)和低的密度(0.534 g·cm^(−3)),被认为是最具潜力的负极材料。但循环过程中不可控的枝晶生长及不稳定的固体电解质相界面膜所引起的安全隐患和电池库伦效率低等问题严重阻碍了锂金属负极的发展。通过在电极表面构建人造保护膜可以有效调控锂离子沉积行为,因此人造保护膜的构建是一种简单高效抑制锂枝晶生长的策略。本综述将从聚合物保护膜、无机保护膜、有机-无机复合保护膜和合金保护膜总结了人造保护膜的构建方法、抑制锂枝晶生长机理,为促进高比能锂金属电池的商业化应用提供借鉴参考作用。展开更多
Lithium metal has been considered to be the most promising anode material for the new generation of energy-storage system.However,challenges still stand in protecting lithium metal from spontaneous reactions with elec...Lithium metal has been considered to be the most promising anode material for the new generation of energy-storage system.However,challenges still stand in protecting lithium metal from spontaneous reactions with electrolytes and preventing the dendritic propagation,both of which would lead to undesirable decrease in Coulombic efficiency.Polysulfone(PSf)membrane with high rigidity and free-volume cavities of approximately 0.3 nm was employed to provide a stable interface on the surface of anodic electrode.The isotropic channels were constructed by the interconnected and uniformly distributed free volumes in the polymer matrix,and were expected to be swelled by solvent molecules and anions of lithium salt and to allow Li+ions to pass through onto the electrode surface.As a result,dendrite-free morphology of deposited lithium was observed.The stabilized interface arose from the PSf film was verified by the promoted performances of Cu|Li cells and steady voltage polarization of Li|Li cells.The full cell with PSf coated anode exhibited excellent cyclability(85%capacity retention rate over 400 cycles at 1C)and an outstanding rate capability(117 m Ah g-1 at 5C).The beneficial performances were further verified by the EIS results.This work provides a new strategic idea to settle the dendritic problems of Li metal anodes.展开更多
基金supported by the National Key Research and Development Program (no.2016YFA0202500)National Basic Research Program of China (2015CB932500)the Natural Scientific Foundation of China (nos.21306102 and 21422604)
文摘Nanostructured materials have received tremendous interest due to their unique mechanical/electrical properties and overall behavior contributed by the complex synergy of bulk and interfacial properties for efficient and effective energy conversion and storage. The booming development of nanotechnology affords emerging but effective tools in designing advanced energy material. We reviewed the significant progress and dominated nanostructured energy materials in electrochemical energy conversion and storage devices, including lithium ion batteries, lithium-sulfur batteries, lithium-oxygen batteries, lithium metal batteries, and supercapacitors. The use of nanostructured electrocatalyst for effective electrocatalysis in oxygen reduction and oxygen evolution reactions for fuel cells and metal-air batteries was also included. The challenges in the undesirable side reactions between electrolytes and electrode due to high electrode/electrolyte contact area, low volumetric energy density of electrode owing to low tap density, and uniform production of complex energy materials in working devices should be overcome to fully demonstrate the advanced energy nanostructures for electrochemical energy conversion and storage. The energy chemistry at the interfaces of nanostructured electrode/electrolyte is highly expected to guide the rational design and full demonstration of energy materials in a working device. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.
文摘金属锂具有高理论比容量和低氧化还原电位,被认为是高能量密度二次电池最理想的负极材料之一,但其在循环过程中的枝晶生长和体积变化易造成电池失效和安全隐患.以孔径为 5 μm 左右的自制三维多孔铜为基底,在其表面电沉积锌层(3D Cu@Zn),作为金属锂沉积的集流体,构筑无枝晶锂金属电极.三维多孔铜的孔结构稳定,孔径大小适宜,可有效降低局部电流密度和缓解体积变化.锌镀层可降低锂金属的形核过电位,诱导锂的均匀沉积,有效抑制锂枝晶生长.以 3D Cu@Zn 为集流体,锂沉积面积容量为 4 m Ah·cm^(-2),电极表面仍无枝晶出现,经过锂剥离后表面仍然光滑;而铜箔上沉积的锂显示明显的枝晶和不均匀性,3D Cu 上沉积的锂显示局部不均匀性和一定量枝晶.在电流密度为 0.5 和 1m A·cm^(-2),面积容量为 1 m Ah·cm^(-2)条件下,Li||3D Cu@Zn 半电池获得了稳定的库伦效率;在 2 m A·cm^(-2)的高电流密度和 1 m Ah·cm^(-2)的面积容量条件下,Li||3D Cu@Zn@Li 对称电池可稳定循环 700 h 以上;以 3D Cu@Zn@Li 为负极,Li Fe PO_(4)为正极的全电池,在 1 C 倍率下,经过 150 次循环后仍保持 88 m Ah·g^(-1)的容量,均明显优于 Cu 片和 3D Cu 作为集流体的锂金属电极.
文摘金属锂因其具有极高的理论容量(3860 mAh·g^(−1))、最低的电极电位(−3.04 V vs.标准氢电极)和低的密度(0.534 g·cm^(−3)),被认为是最具潜力的负极材料。但循环过程中不可控的枝晶生长及不稳定的固体电解质相界面膜所引起的安全隐患和电池库伦效率低等问题严重阻碍了锂金属负极的发展。通过在电极表面构建人造保护膜可以有效调控锂离子沉积行为,因此人造保护膜的构建是一种简单高效抑制锂枝晶生长的策略。本综述将从聚合物保护膜、无机保护膜、有机-无机复合保护膜和合金保护膜总结了人造保护膜的构建方法、抑制锂枝晶生长机理,为促进高比能锂金属电池的商业化应用提供借鉴参考作用。
基金supported by the Opening Project(SKLACPS-C-21)of the State Key Laboratory of Advanced Chemical Power Source,Guizhou Meiling Power Sources Co.Ltd.the Program for Innovative and Entrepreneurial team in Zhuhai(ZH01110405160007PWC)Key Laboratory of Advanced Chemical Power Sources,Guizhou Meiling Power Sources Co.Ltd.,Zunyi 563003,Guizhou,China,for funding the experiments.
文摘Lithium metal has been considered to be the most promising anode material for the new generation of energy-storage system.However,challenges still stand in protecting lithium metal from spontaneous reactions with electrolytes and preventing the dendritic propagation,both of which would lead to undesirable decrease in Coulombic efficiency.Polysulfone(PSf)membrane with high rigidity and free-volume cavities of approximately 0.3 nm was employed to provide a stable interface on the surface of anodic electrode.The isotropic channels were constructed by the interconnected and uniformly distributed free volumes in the polymer matrix,and were expected to be swelled by solvent molecules and anions of lithium salt and to allow Li+ions to pass through onto the electrode surface.As a result,dendrite-free morphology of deposited lithium was observed.The stabilized interface arose from the PSf film was verified by the promoted performances of Cu|Li cells and steady voltage polarization of Li|Li cells.The full cell with PSf coated anode exhibited excellent cyclability(85%capacity retention rate over 400 cycles at 1C)and an outstanding rate capability(117 m Ah g-1 at 5C).The beneficial performances were further verified by the EIS results.This work provides a new strategic idea to settle the dendritic problems of Li metal anodes.
