Oxygen anion redox reaction provides a high theoretical capacity for Li-rich manganese-based cathodes.However,irreversible surface oxygen release often results in further oxygen loss and exacerbates the decomposition ...Oxygen anion redox reaction provides a high theoretical capacity for Li-rich manganese-based cathodes.However,irreversible surface oxygen release often results in further oxygen loss and exacerbates the decomposition of the electrolyte,which could reduce the capacity contribution from the anionic redox and produce more acidic substances to corrode the surface of the material.In this paper,the surface oxygen release is suppressed by moderating oxygen anion redox activity via constructing chemical bonds between M(M=Fe and La)in LaFeO_(3)and surface oxygen anions of Li_(1.2)Mn_(0.6)Ni_(0.2)O_(2).The constructed interface layer stabilizes the surface lattice oxygen and retards the electrolyte from being attacked by the nucleophilic oxygen generated in the process of oxygen release,as evidenced by Differential Electrochemical Mass Spectrometry(DEMS)and X-ray Photoelectron Spectroscopy(XPS)detections.Moreover,in the charge and discharge process,the formed FeF_(3),located at the cathode electrolyte interfacial layer,is conducive to the stability of the cathode surface.The modified Li_(1.2)Mn_(0.6)Ni_(0.2)O_(2)electrode with 3 wt%LaFeO_(13)exhibits a high specific capacity of 189.5 mA h g-at 1C(200 mA g^(-1))after 150 cycles with capacity retentions of 96.6%,and 112.6 mA h g^(-1)(84.7%)at 5C after 200 cycles higher than the pristine sample.This study provides a rational design chemical bonding method to suppress the oxygen release from the cathode surface and enhance cyclic stability.展开更多
Lithium(Li)-rich manganese(Mn)-based cathode Li_(1.2)Ni_(0.13)Co_(0.13)Mn_(0.54)O_(2)(LRNCM)has attracted considerable attention owing to its high specific discharge capacity and low cost.However,unsatisfactory cycle ...Lithium(Li)-rich manganese(Mn)-based cathode Li_(1.2)Ni_(0.13)Co_(0.13)Mn_(0.54)O_(2)(LRNCM)has attracted considerable attention owing to its high specific discharge capacity and low cost.However,unsatisfactory cycle performance and poor rate property hinder its large-scale application.The fast ionic conductor has been widely used as the cathode coating material because of its superior stability and excellent lithium-ion conductivity rate.In this study,Li_(1.2)Ni_(0.13)Co_(0.13)Mn_(0.54)O_(2) is modified by using Li_(1.4)Al_(0.4)Ti_(1.6)(PO_(4))_(3)(LATP)ionic conductor.The electrochemical test results show that the discharge capacity of the resulting LRNCM@LATP1 sample is 198 mA·h/g after 100 cycles at 0.2C,with a capacity retention of 81%.Compared with the uncoated pristine LRNCM(188.4 m A·h/g and 76%),LRNCM after the LATP modification shows superior cycle performance.Moreover,the lithium-ion diffusion coefficient D_(Li+)is a crucial factor affecting the rate performance,and the D_(Li+)of the LRNCM material is improved from 4.94×10^(-13) to 5.68×10^(-12)cm^(2)/s after modification.The specific capacity of LRNCM@LATP1 reaches 102.5 mA·h/g at 5C,with an improved rate performance.Thus,the modification layer can considerably enhance the electrochemical performance of LRNCM.展开更多
基金supported by the National Natural Science Foundation of China(22175070,22293041,51902081,and 21871106)Key Fund in Hebei Province Department of Education China(ZD2022042)。
文摘Oxygen anion redox reaction provides a high theoretical capacity for Li-rich manganese-based cathodes.However,irreversible surface oxygen release often results in further oxygen loss and exacerbates the decomposition of the electrolyte,which could reduce the capacity contribution from the anionic redox and produce more acidic substances to corrode the surface of the material.In this paper,the surface oxygen release is suppressed by moderating oxygen anion redox activity via constructing chemical bonds between M(M=Fe and La)in LaFeO_(3)and surface oxygen anions of Li_(1.2)Mn_(0.6)Ni_(0.2)O_(2).The constructed interface layer stabilizes the surface lattice oxygen and retards the electrolyte from being attacked by the nucleophilic oxygen generated in the process of oxygen release,as evidenced by Differential Electrochemical Mass Spectrometry(DEMS)and X-ray Photoelectron Spectroscopy(XPS)detections.Moreover,in the charge and discharge process,the formed FeF_(3),located at the cathode electrolyte interfacial layer,is conducive to the stability of the cathode surface.The modified Li_(1.2)Mn_(0.6)Ni_(0.2)O_(2)electrode with 3 wt%LaFeO_(13)exhibits a high specific capacity of 189.5 mA h g-at 1C(200 mA g^(-1))after 150 cycles with capacity retentions of 96.6%,and 112.6 mA h g^(-1)(84.7%)at 5C after 200 cycles higher than the pristine sample.This study provides a rational design chemical bonding method to suppress the oxygen release from the cathode surface and enhance cyclic stability.
基金Project(51772333) supported by the National Natural Science Foundation of China。
文摘Lithium(Li)-rich manganese(Mn)-based cathode Li_(1.2)Ni_(0.13)Co_(0.13)Mn_(0.54)O_(2)(LRNCM)has attracted considerable attention owing to its high specific discharge capacity and low cost.However,unsatisfactory cycle performance and poor rate property hinder its large-scale application.The fast ionic conductor has been widely used as the cathode coating material because of its superior stability and excellent lithium-ion conductivity rate.In this study,Li_(1.2)Ni_(0.13)Co_(0.13)Mn_(0.54)O_(2) is modified by using Li_(1.4)Al_(0.4)Ti_(1.6)(PO_(4))_(3)(LATP)ionic conductor.The electrochemical test results show that the discharge capacity of the resulting LRNCM@LATP1 sample is 198 mA·h/g after 100 cycles at 0.2C,with a capacity retention of 81%.Compared with the uncoated pristine LRNCM(188.4 m A·h/g and 76%),LRNCM after the LATP modification shows superior cycle performance.Moreover,the lithium-ion diffusion coefficient D_(Li+)is a crucial factor affecting the rate performance,and the D_(Li+)of the LRNCM material is improved from 4.94×10^(-13) to 5.68×10^(-12)cm^(2)/s after modification.The specific capacity of LRNCM@LATP1 reaches 102.5 mA·h/g at 5C,with an improved rate performance.Thus,the modification layer can considerably enhance the electrochemical performance of LRNCM.
