LiNiO_(2)(LNO)is one of the most promising cathode materials for lithium-ion batteries.Tungsten element in enhancing the stability of LNO has been researched extensively.However,the understanding of the specific dopin...LiNiO_(2)(LNO)is one of the most promising cathode materials for lithium-ion batteries.Tungsten element in enhancing the stability of LNO has been researched extensively.However,the understanding of the specific doping process and existing form of W are still not perfect.This study proposes a lithium-induced grain boundary phase W doping mechanism.The results demonstrate that the introduced W atomsfirst react with the lithium source to generate a Li–W–O phase at the grain boundary of primary particles.With the increase of lithium ratio,W atoms gradually diffuse from the grain boundary phase to the interior layered structure to achieve W doping.The feasibility of grain boundary phase doping is verified byfirst principles calculation.Furthermore,it is found that the Li2WO4 grain boundary phase is an excellent lithium ion conductor,which can protect the cathode surface and improve the rate performance.The doped W can alleviate the harmful H2↔H3 phase transition,thereby inhibiting the generation of microcracks,and improving the electrochemical performance.Consequently,the 0.3 wt%W-doped sample provides a significant improved capacity retention of 88.5%compared with the pristine LNO(80.7%)after 100 cycles at 2.8–4.3 V under 1C.展开更多
基金supported by the National Natural Science Foundation of China(No.52122407,No.52174285,52404317)the Science and Technology Innovation Program of Hunan Province(No.2022RC3048).
文摘LiNiO_(2)(LNO)is one of the most promising cathode materials for lithium-ion batteries.Tungsten element in enhancing the stability of LNO has been researched extensively.However,the understanding of the specific doping process and existing form of W are still not perfect.This study proposes a lithium-induced grain boundary phase W doping mechanism.The results demonstrate that the introduced W atomsfirst react with the lithium source to generate a Li–W–O phase at the grain boundary of primary particles.With the increase of lithium ratio,W atoms gradually diffuse from the grain boundary phase to the interior layered structure to achieve W doping.The feasibility of grain boundary phase doping is verified byfirst principles calculation.Furthermore,it is found that the Li2WO4 grain boundary phase is an excellent lithium ion conductor,which can protect the cathode surface and improve the rate performance.The doped W can alleviate the harmful H2↔H3 phase transition,thereby inhibiting the generation of microcracks,and improving the electrochemical performance.Consequently,the 0.3 wt%W-doped sample provides a significant improved capacity retention of 88.5%compared with the pristine LNO(80.7%)after 100 cycles at 2.8–4.3 V under 1C.
