在众多Na离子电池正极材料中,P2型层状氧化物因其优异的动力学性能受到研究者们的广泛关注。在P2型层状氧化物材料中,Na离子有2种不同的位点,即Na_(e)和Na_(f)。由于配位环境的差异,Na离子在不同位点间的迁移行为不同。本工作提出通过...在众多Na离子电池正极材料中,P2型层状氧化物因其优异的动力学性能受到研究者们的广泛关注。在P2型层状氧化物材料中,Na离子有2种不同的位点,即Na_(e)和Na_(f)。由于配位环境的差异,Na离子在不同位点间的迁移行为不同。本工作提出通过调控材料中Na含量的策略实现了对同一过渡金属组分材料的/Na_(f)位点占位比的优化。研究发现,与Na_(0.45)Ni_(0.1)Mn_(0.9)O_(2)和Na_(0.65)Ni_(0.1)Mn_(0.9)O_(2)相比,具有更高Na_(e)/Na_(f)位点占比值的Na_(0.55)Ni_(0.1)Mn_(0.9)O_(2)材料表现出最为优异的电化学性能,其电化学曲线平滑,在0.2 C (1 C=173 m A·g^(-1))的倍率下容量高达174.5 m A·h·g^(-1),在3 C,循环200次容量保持率高达92.95%,10 C的高倍率下仍能发挥83.6 mA·h·g^(-1)的容量,该策略为设计高性能P2型钠电正极材料打开了新的思路。展开更多
O3-type layered oxides have garnered great attention as cathode materials for sodium-ion batteries because of their abundant reserves and high theoretical capacity.However,challenges persist in the form of uncontrolla...O3-type layered oxides have garnered great attention as cathode materials for sodium-ion batteries because of their abundant reserves and high theoretical capacity.However,challenges persist in the form of uncontrollable phase transitions and intricate Na^(+)diffusion pathways during cycling,resulting in compromised structural stability and reduced capacity over cycles.This study introduces a special approach employing site-specific Ca/F co-substitution within the layered structure of O_(3)-NaNi_(0.5)Mn_(0.5)O_(2) to effectively address these issues.Herein,the strategically site-specific doping of Ca into Na sites and F into O sites not only expands the Na^(+)diffusion pathways but also orchestrates a mild phase transition by suppressing the Na^(+)/vacancy ordering and providing strong metal-oxygen bonding strength,respectively.The as-synthesized Na_(0.95)Ca_(0.05)Ni_(0.5)Mn_(0.5)O_(1.95)F_(0.05)(NNMO-CaF)exhibits a mild O3→O3+O'3→P3 phase transition with minimized interlayer distance variation,leading to enhanced structural integrity and stability over extended cycles.As a result,NNMO-CaF delivers a high specific capacity of 119.5 mA h g^(-1)at a current density of 120 mA g^(-1)with a capacity retention of 87.1%after 100 cycles.This study presents a promising strategy to mitigate the challenges posed by multiple phase transitions and augment Na^(+)diffusion kinetics,thus paving the way for high-performance layered cathode materials in sodium-ion batteries.展开更多
Na_(0.5)(Bi_(3/4)RE_(1/4))_(0.5)TiO_(3)(RENBT,RE=Nd,Gd,Dy,and Ho)compounds were investigated in the framework of first-principles calculations using the full potential linearized augmented plane wave(FP-LAPW)method ba...Na_(0.5)(Bi_(3/4)RE_(1/4))_(0.5)TiO_(3)(RENBT,RE=Nd,Gd,Dy,and Ho)compounds were investigated in the framework of first-principles calculations using the full potential linearized augmented plane wave(FP-LAPW)method based on the spin-polarized density functional theory implemented in the WIEN2k code.Combined charge density distribution and Ti K-edge X-ray absorption spectra reveal that the RENBT compositions with high polarization values are accompanied by a higher TiO_(6)distortion,DyNBT,and NdNBT compounds.The effect of the rare-earth elements on the polarization is confirmed experimentally with the collection of the hysteresis loops.The investigation of the electronic properties of the compounds highlights the emergence of a magnetization owing to the 4f orbital effect of the rare-earth elements.Besides,the investigation of the chemical ordering shows a short-range chemical ordering for the pure composition and an increased A-site disorder for dysprosium doped NBT system.The increased disorder may speak for increased relaxor properties in the RE doped compositions.展开更多
文摘在众多Na离子电池正极材料中,P2型层状氧化物因其优异的动力学性能受到研究者们的广泛关注。在P2型层状氧化物材料中,Na离子有2种不同的位点,即Na_(e)和Na_(f)。由于配位环境的差异,Na离子在不同位点间的迁移行为不同。本工作提出通过调控材料中Na含量的策略实现了对同一过渡金属组分材料的/Na_(f)位点占位比的优化。研究发现,与Na_(0.45)Ni_(0.1)Mn_(0.9)O_(2)和Na_(0.65)Ni_(0.1)Mn_(0.9)O_(2)相比,具有更高Na_(e)/Na_(f)位点占比值的Na_(0.55)Ni_(0.1)Mn_(0.9)O_(2)材料表现出最为优异的电化学性能,其电化学曲线平滑,在0.2 C (1 C=173 m A·g^(-1))的倍率下容量高达174.5 m A·h·g^(-1),在3 C,循环200次容量保持率高达92.95%,10 C的高倍率下仍能发挥83.6 mA·h·g^(-1)的容量,该策略为设计高性能P2型钠电正极材料打开了新的思路。
基金supported by the Science and Technology Program of Suzhou(ST202304)the National Natural Science Foundation of China(12275189)+1 种基金the Collaborative Innovation Center of Suzhou Nano Science&Technologythe 111 project。
文摘O3-type layered oxides have garnered great attention as cathode materials for sodium-ion batteries because of their abundant reserves and high theoretical capacity.However,challenges persist in the form of uncontrollable phase transitions and intricate Na^(+)diffusion pathways during cycling,resulting in compromised structural stability and reduced capacity over cycles.This study introduces a special approach employing site-specific Ca/F co-substitution within the layered structure of O_(3)-NaNi_(0.5)Mn_(0.5)O_(2) to effectively address these issues.Herein,the strategically site-specific doping of Ca into Na sites and F into O sites not only expands the Na^(+)diffusion pathways but also orchestrates a mild phase transition by suppressing the Na^(+)/vacancy ordering and providing strong metal-oxygen bonding strength,respectively.The as-synthesized Na_(0.95)Ca_(0.05)Ni_(0.5)Mn_(0.5)O_(1.95)F_(0.05)(NNMO-CaF)exhibits a mild O3→O3+O'3→P3 phase transition with minimized interlayer distance variation,leading to enhanced structural integrity and stability over extended cycles.As a result,NNMO-CaF delivers a high specific capacity of 119.5 mA h g^(-1)at a current density of 120 mA g^(-1)with a capacity retention of 87.1%after 100 cycles.This study presents a promising strategy to mitigate the challenges posed by multiple phase transitions and augment Na^(+)diffusion kinetics,thus paving the way for high-performance layered cathode materials in sodium-ion batteries.
基金Project supported by the Haute France Region/FEDER(project MASEN)H2020-RISE-ENGIMA-778072 project。
文摘Na_(0.5)(Bi_(3/4)RE_(1/4))_(0.5)TiO_(3)(RENBT,RE=Nd,Gd,Dy,and Ho)compounds were investigated in the framework of first-principles calculations using the full potential linearized augmented plane wave(FP-LAPW)method based on the spin-polarized density functional theory implemented in the WIEN2k code.Combined charge density distribution and Ti K-edge X-ray absorption spectra reveal that the RENBT compositions with high polarization values are accompanied by a higher TiO_(6)distortion,DyNBT,and NdNBT compounds.The effect of the rare-earth elements on the polarization is confirmed experimentally with the collection of the hysteresis loops.The investigation of the electronic properties of the compounds highlights the emergence of a magnetization owing to the 4f orbital effect of the rare-earth elements.Besides,the investigation of the chemical ordering shows a short-range chemical ordering for the pure composition and an increased A-site disorder for dysprosium doped NBT system.The increased disorder may speak for increased relaxor properties in the RE doped compositions.
基金grants from the National Natural Science Foundation of China(No.82074162,81903995)the Young Elite Scientists Sponsorship Program by CACM(No.CACM-2019-QNRC2-C10)+1 种基金Science and Technology Innovation Project of Putuo District Health System(No.ptkwws201902,ptkwws201908,ptkwws202009,ptkwws202107)and Research Project(No.2019307,2020308A)the One Hundred Talents(No.2022-RCLH-02)of Putuo Hospital,Shanghai University of Traditional Chinese Medicine。
