Na-based layered transition metal oxides with O_(3)-type structure have been considered to be promising cathodes for Na-ion batteries. However, the intrinsically limited Na-ion conductivity induced by the Otype Na-coo...Na-based layered transition metal oxides with O_(3)-type structure have been considered to be promising cathodes for Na-ion batteries. However, the intrinsically limited Na-ion conductivity induced by the Otype Na-coordinate environment compromises their rate and cycle capability, hindering their practical application. Here, we report an interphase-structure tailoring strategy that improves the electrochemical properties of O_(3)-type layered cathodes achieved through surface coating and doping processes.Specifically, a Zr-doped interphase structure is designed in the model compound NaNi_(1/3)Mn_(1/3)Fe_(1/3)O_(2) using the ionic conductor Na_(3)Zr_(2)Si_(2)PO_(12) as the surface coating material and Zr-dopant provider. We discover that the modified NaNi_(1/3)Mn_(1/3)Fe_(1/3)O_(2)cathode shows a stable Na-storage structure as well as an enhanced rate/cycle capability. Combined with theoretical calculations, it is suggested that the superior electrochemical performances originate from the Zr-doped interphase structure, which has an enlarged Na layer spacing that forms favorable Na-ion diffusion channels. This work highlights a general material interface optimization method which opens a new perspective for fabricating high-performance electrodes for Na-ion batteries and beyond.展开更多
Na-based layered iron-manganese oxide Na_(0.67)Fe_(0.5)Mn_(0.5)O_(2) containing only low-cost elements is a promising cathode for Na-ion batteries used in large-scale energy storage systems.However,the poor cycle stab...Na-based layered iron-manganese oxide Na_(0.67)Fe_(0.5)Mn_(0.5)O_(2) containing only low-cost elements is a promising cathode for Na-ion batteries used in large-scale energy storage systems.However,the poor cycle stability restricts its practical application.The capacity decay of Na_(0.67)Fe_(0.6)Mn_(0.5)O_(2) mainly originates from the irreversible anionic redox reaction charge compensation due to the high-level hybridization between oxygen and iron.Herein,we rationally design a surface Ti doping strategy to tune the anionic redox reaction activity of Na_(0.67)Fe_(0.5)Mn_(0.5)O_(2) and improve its Na-storage properties.The doped Ti ions not only enlarge the Na migration spacing layer but also improve the structure stability thanks to the strong Ti-O bond.More importantly,the d0-shell electronic structure of Ti^(4+) can suppress the charge transfer from the oxidized anions to cations,thus reducing the anionic redox reaction activity and enhancing the reversibility of charge compensation.The modified Na_(0.67)Fe_(0.5)Mn_(0.5)O_(2) cathode shows a reversible capacity of 198 mA h g^(-1) and an increased capacity retention from 15% to 73% after about1 month of cycling.Meanwhile,a superior Na-ion diffusion kinetics and rate capability are also observed.This work advances the commercialization process of Na-based layered iron-manganese oxide cathodes;on the other hand,the proposed modification strategy paves the way for the design of high-performance electrode materials relying on anionic redox reactions.展开更多
Nickel-rich cathode materials have attracted considerable interest because of their high specific capacities,voltage ranges,and low cost.However,serious capacity attenuation and poor rate performance limit their appli...Nickel-rich cathode materials have attracted considerable interest because of their high specific capacities,voltage ranges,and low cost.However,serious capacity attenuation and poor rate performance limit their application.This study proposes a novel strategy to improve the cycle stability of the nickel-rich LiNi0.sCo0.1Mn0.1O2(NCM811)layer material by designing core-shell LiNio.sCoo.1 Mno.102(CS-NCM811).CS-NCM811 is designed by the characteristic reaction between dimethylglyoxime(C4H8N2O2)and nickel ion to form Ni(C4H7N2O2)2-The CS-NCM811 is characterized with high nickel content in its core and high manganese content on its surface,leading to a high capacity and excellent cycle stability.The capacity retention of CS-NCM811 was 72.8%,much higher than that of NCM811(47.1%)after 500 cycles at a rate of 5 C.Not only is this method a no vel strategy to desig n high capacity cathode materials but also provides some new in sights into the cycle stability of nickel-rich layered cathode materials.展开更多
Solid and hollow microspheres of LiMn_(2)O_(4) have been synthesized by lithiating MnCO_(3) solid microspheres and MnO_(2) hollow microspheres,respectively.The LiMn_(2)O_(4) solid microspheres and hollow microspheres ...Solid and hollow microspheres of LiMn_(2)O_(4) have been synthesized by lithiating MnCO_(3) solid microspheres and MnO_(2) hollow microspheres,respectively.The LiMn_(2)O_(4) solid microspheres and hollow microspheres had a similar size of about 1.5μm,and the shell thickness of the hollow microspheres was only 100 nm.When used as a cathode material in lithium ion batteries,the hollow microspheres exhibited better rate capability than the solid microspheres.However,the tap density of the LiMn_(2)O_(4) solid microspheres(1.0 g/cm^(3))was about four times that of the hollow microspheres(0.27 g/cm^(3)).The results show that controlling the particle size of LiMn_(2)O_(4) is very important in terms of its practical application as a cathode material,and LiMn_(2)O_(4) with moderate particle size may afford acceptable values of both rate capability and tap density.展开更多
Orthorhombic LiMnO_(2)nanoparticles and LiMnO_(2)nanorods have been synthesized by hydrothermal methods.LiMnO_(2)nanoparticles were synthesized by simple one-step hydrothermal method.To obtain rod-like LiMnO_(2),γ-Mn...Orthorhombic LiMnO_(2)nanoparticles and LiMnO_(2)nanorods have been synthesized by hydrothermal methods.LiMnO_(2)nanoparticles were synthesized by simple one-step hydrothermal method.To obtain rod-like LiMnO_(2),γ-MnOOH nanorods were first synthesized and then the H+ions were completely replaced by Li+resulting in LiMnO_(2)nanorods.Their electrochemical performances were thoroughly investigated by galvanostatic tests.Although the LiMnO_(2)nanoparticles have smaller size than LiMnO_(2)nanorods,the latter exhibited higher discharge capacity and better cyclability.For example,the discharge capacities of LiMnO_(2)nanorods reached 200 mA·h/g over many cycles and remained above 180 mA·h/g after 30 cycles.However,the maximum capacity of LiMnO_(2)nanoparticles was only 170 mA·h/g and quickly decreased to 110 mA·h/g after 30 cycles.Nanorods with one-dimensional electronic pathways favor the transport of electrons along the length direction and accommodate volume changes resulting from charge/discharge processes.Thus the morphology of LiMnO_(2)may play an important role in electrochemical performance.展开更多
基金The University of Chinese Academy of Sciences,and the Scientific Instrument Developing Project of the Chinese Academy of Sciences (ZDKYYQ20170001):China the Guangdong Basic and Applied Basic Research Foundation (2019A1515111025) China the Japan Synchrotron Radiation Research Institute (2019B1096)Japan。
文摘Na-based layered transition metal oxides with O_(3)-type structure have been considered to be promising cathodes for Na-ion batteries. However, the intrinsically limited Na-ion conductivity induced by the Otype Na-coordinate environment compromises their rate and cycle capability, hindering their practical application. Here, we report an interphase-structure tailoring strategy that improves the electrochemical properties of O_(3)-type layered cathodes achieved through surface coating and doping processes.Specifically, a Zr-doped interphase structure is designed in the model compound NaNi_(1/3)Mn_(1/3)Fe_(1/3)O_(2) using the ionic conductor Na_(3)Zr_(2)Si_(2)PO_(12) as the surface coating material and Zr-dopant provider. We discover that the modified NaNi_(1/3)Mn_(1/3)Fe_(1/3)O_(2)cathode shows a stable Na-storage structure as well as an enhanced rate/cycle capability. Combined with theoretical calculations, it is suggested that the superior electrochemical performances originate from the Zr-doped interphase structure, which has an enlarged Na layer spacing that forms favorable Na-ion diffusion channels. This work highlights a general material interface optimization method which opens a new perspective for fabricating high-performance electrodes for Na-ion batteries and beyond.
基金supported by the National Natural Science Foundation of China (Grant No. 12105197)the Science Center of the National Science Foundation of China (Grant No. 52088101)+1 种基金the Fundamental Research Funds for the Central Universitiesthe Scientific Instrument Developing Project of the Chinese Academy of Sciences (Grant ZDKYYQ20170001)。
文摘Na-based layered iron-manganese oxide Na_(0.67)Fe_(0.5)Mn_(0.5)O_(2) containing only low-cost elements is a promising cathode for Na-ion batteries used in large-scale energy storage systems.However,the poor cycle stability restricts its practical application.The capacity decay of Na_(0.67)Fe_(0.6)Mn_(0.5)O_(2) mainly originates from the irreversible anionic redox reaction charge compensation due to the high-level hybridization between oxygen and iron.Herein,we rationally design a surface Ti doping strategy to tune the anionic redox reaction activity of Na_(0.67)Fe_(0.5)Mn_(0.5)O_(2) and improve its Na-storage properties.The doped Ti ions not only enlarge the Na migration spacing layer but also improve the structure stability thanks to the strong Ti-O bond.More importantly,the d0-shell electronic structure of Ti^(4+) can suppress the charge transfer from the oxidized anions to cations,thus reducing the anionic redox reaction activity and enhancing the reversibility of charge compensation.The modified Na_(0.67)Fe_(0.5)Mn_(0.5)O_(2) cathode shows a reversible capacity of 198 mA h g^(-1) and an increased capacity retention from 15% to 73% after about1 month of cycling.Meanwhile,a superior Na-ion diffusion kinetics and rate capability are also observed.This work advances the commercialization process of Na-based layered iron-manganese oxide cathodes;on the other hand,the proposed modification strategy paves the way for the design of high-performance electrode materials relying on anionic redox reactions.
文摘Nickel-rich cathode materials have attracted considerable interest because of their high specific capacities,voltage ranges,and low cost.However,serious capacity attenuation and poor rate performance limit their application.This study proposes a novel strategy to improve the cycle stability of the nickel-rich LiNi0.sCo0.1Mn0.1O2(NCM811)layer material by designing core-shell LiNio.sCoo.1 Mno.102(CS-NCM811).CS-NCM811 is designed by the characteristic reaction between dimethylglyoxime(C4H8N2O2)and nickel ion to form Ni(C4H7N2O2)2-The CS-NCM811 is characterized with high nickel content in its core and high manganese content on its surface,leading to a high capacity and excellent cycle stability.The capacity retention of CS-NCM811 was 72.8%,much higher than that of NCM811(47.1%)after 500 cycles at a rate of 5 C.Not only is this method a no vel strategy to desig n high capacity cathode materials but also provides some new in sights into the cycle stability of nickel-rich layered cathode materials.
基金This work was supported by the State Key Project of Fundamental Research for Nanoscience and Nanotechnology （Nos. 2011CB932401, 2011CBA00500, and 2012CB224802）, and the National Natural Science Foundation of China （Nos. 21221062, 21131004, and 21390393）. The authors thank Electron Microscopy Laboratory of Peking University for the help with HRTEM analysis.
基金This work was supported by the National Nature Science Foundation of China(NSFC)(Nos.20921001 and 90606006)the Tsinghua University Initiative Scientific Research Program(No.2009HTZ08).
文摘Solid and hollow microspheres of LiMn_(2)O_(4) have been synthesized by lithiating MnCO_(3) solid microspheres and MnO_(2) hollow microspheres,respectively.The LiMn_(2)O_(4) solid microspheres and hollow microspheres had a similar size of about 1.5μm,and the shell thickness of the hollow microspheres was only 100 nm.When used as a cathode material in lithium ion batteries,the hollow microspheres exhibited better rate capability than the solid microspheres.However,the tap density of the LiMn_(2)O_(4) solid microspheres(1.0 g/cm^(3))was about four times that of the hollow microspheres(0.27 g/cm^(3)).The results show that controlling the particle size of LiMn_(2)O_(4) is very important in terms of its practical application as a cathode material,and LiMn_(2)O_(4) with moderate particle size may afford acceptable values of both rate capability and tap density.
基金the National Natural Science Foundation of China(No.90606006)the State Key Project of Fundamental Research for Nanoscience and Nanotechnology(No.2006CB932300).
文摘Orthorhombic LiMnO_(2)nanoparticles and LiMnO_(2)nanorods have been synthesized by hydrothermal methods.LiMnO_(2)nanoparticles were synthesized by simple one-step hydrothermal method.To obtain rod-like LiMnO_(2),γ-MnOOH nanorods were first synthesized and then the H+ions were completely replaced by Li+resulting in LiMnO_(2)nanorods.Their electrochemical performances were thoroughly investigated by galvanostatic tests.Although the LiMnO_(2)nanoparticles have smaller size than LiMnO_(2)nanorods,the latter exhibited higher discharge capacity and better cyclability.For example,the discharge capacities of LiMnO_(2)nanorods reached 200 mA·h/g over many cycles and remained above 180 mA·h/g after 30 cycles.However,the maximum capacity of LiMnO_(2)nanoparticles was only 170 mA·h/g and quickly decreased to 110 mA·h/g after 30 cycles.Nanorods with one-dimensional electronic pathways favor the transport of electrons along the length direction and accommodate volume changes resulting from charge/discharge processes.Thus the morphology of LiMnO_(2)may play an important role in electrochemical performance.
