P2型层状过渡金属氧化物(P2-Na_(x)TMO_(2))因其优异的循环稳定性和倍率性能,成为钠离子电池正极材料的有力候选者。然而,其在高电压下的不可逆相变和固有低理论容量问题,阻碍了实际应用。本研究工作提出高熵策略与双相结构的协同设计...P2型层状过渡金属氧化物(P2-Na_(x)TMO_(2))因其优异的循环稳定性和倍率性能,成为钠离子电池正极材料的有力候选者。然而,其在高电压下的不可逆相变和固有低理论容量问题,阻碍了实际应用。本研究工作提出高熵策略与双相结构的协同设计来克服这些挑战。通过在P2相高熵基体中引入O3相,构建新型P2/O3双相高熵层状氧化物Na_(0.70)Ni_(0.25)Mn_(0.35)Co_(0.15)Fe_(0.05)Ti_(0.20)O_(2)(简称Na_(0.70)NMCFT)。其中,高熵设计通过构型熵稳定效应有效抑制P2相的不可逆相变,而O3相则通过协同作用弥补容量不足并提升循环稳定性。此外,双相组分之间的相互作用进一步促进P2-O3与P2-P3相变的高度可逆性。Na_(0.70)NMCFT在1C倍率下的初始放电容量为102.08 mAhg^(-1),200次循环后容量保持率达88.15%,表明具有优异的循环稳定性。更重要的是,即使在10C的高倍率下,Na_(0.70)NMCFT仍能提供85.67 mAh g^(-1)的初始放电比容量,并在1000次循环后容量保持率达70%。本工作证实双相高熵设计在提升钠离子电池正极性能中的关键作用,为开发先进钠离子电池正极材料提供了新思路。展开更多
P2-type nickel-manganese-based layered oxides are promising cathode materials for sodium-ion batteries(SIBs),but their application is limited by initial specific capacity and anion redox instability.Herein,a P2/O3 bip...P2-type nickel-manganese-based layered oxides are promising cathode materials for sodium-ion batteries(SIBs),but their application is limited by initial specific capacity and anion redox instability.Herein,a P2/O3 biphasic Na_(0.67)Ni_(0.33)Mn_(0.6)Cu_(0.05)Mg_(0.07)Ti_(0.01)O_(2)(Ni33Mn60)was prepared by adjusting the Ni/Mn ratio with as Na_(0.67)Ni_(0.23)Mn_(0.65)Cu_(0.05)Mg_(0.07)Ti_(0.01)O_(2)(Ni23Mn65)matrix and is reported to exhibit high initial discharge capacity,cyclability and rate capability.The density functional theory(DFT)calculation and experimental data prove the enhancement of the Mn^(3+)/Mn^(4+)redox process to improve the specific discharge capacity and the P2/O3biphasic structure to optimize the anion kinetics.The synthesized oxide Ni33Mn60 delivers a high initial discharge specific capacity of 140.21 mAh g^(-1),a crucial discharge capacity of 76.07 mAh g^(-1)at 10C,a preferable capacity retention rate of 78.97%after 200 cycles at 5C and cycle stability at high voltages above 4.3V.In situ X-ray diffraction(XRD)and galvanostatic intermittent titration technique(GITT)tests show that Ni33Mn60 has reversible structure evolution and fast Na^(+)diffusion kinetics due to the ion effect and unique P2/O3 biphasic structure,respectively.This work provides a new thought about adjusting matrix ratio for the preparation of P2/O3 biphasic cathode materials for advanced SIBs.展开更多
文摘P2型层状过渡金属氧化物(P2-Na_(x)TMO_(2))因其优异的循环稳定性和倍率性能,成为钠离子电池正极材料的有力候选者。然而,其在高电压下的不可逆相变和固有低理论容量问题,阻碍了实际应用。本研究工作提出高熵策略与双相结构的协同设计来克服这些挑战。通过在P2相高熵基体中引入O3相,构建新型P2/O3双相高熵层状氧化物Na_(0.70)Ni_(0.25)Mn_(0.35)Co_(0.15)Fe_(0.05)Ti_(0.20)O_(2)(简称Na_(0.70)NMCFT)。其中,高熵设计通过构型熵稳定效应有效抑制P2相的不可逆相变,而O3相则通过协同作用弥补容量不足并提升循环稳定性。此外,双相组分之间的相互作用进一步促进P2-O3与P2-P3相变的高度可逆性。Na_(0.70)NMCFT在1C倍率下的初始放电容量为102.08 mAhg^(-1),200次循环后容量保持率达88.15%,表明具有优异的循环稳定性。更重要的是,即使在10C的高倍率下,Na_(0.70)NMCFT仍能提供85.67 mAh g^(-1)的初始放电比容量,并在1000次循环后容量保持率达70%。本工作证实双相高熵设计在提升钠离子电池正极性能中的关键作用,为开发先进钠离子电池正极材料提供了新思路。
基金financially supported by the Natural Science Foundation of Jiangsu Province(No.BK20201049)China Postdoctoral Science Foundation(No,2022M711724)+2 种基金the Swedish Energy Agency(Nos.P2022-00055 and P2023-00603)STandUP for EnergyMAX IV Laboratory for time on Balder beamline(No.20240704)
文摘P2-type nickel-manganese-based layered oxides are promising cathode materials for sodium-ion batteries(SIBs),but their application is limited by initial specific capacity and anion redox instability.Herein,a P2/O3 biphasic Na_(0.67)Ni_(0.33)Mn_(0.6)Cu_(0.05)Mg_(0.07)Ti_(0.01)O_(2)(Ni33Mn60)was prepared by adjusting the Ni/Mn ratio with as Na_(0.67)Ni_(0.23)Mn_(0.65)Cu_(0.05)Mg_(0.07)Ti_(0.01)O_(2)(Ni23Mn65)matrix and is reported to exhibit high initial discharge capacity,cyclability and rate capability.The density functional theory(DFT)calculation and experimental data prove the enhancement of the Mn^(3+)/Mn^(4+)redox process to improve the specific discharge capacity and the P2/O3biphasic structure to optimize the anion kinetics.The synthesized oxide Ni33Mn60 delivers a high initial discharge specific capacity of 140.21 mAh g^(-1),a crucial discharge capacity of 76.07 mAh g^(-1)at 10C,a preferable capacity retention rate of 78.97%after 200 cycles at 5C and cycle stability at high voltages above 4.3V.In situ X-ray diffraction(XRD)and galvanostatic intermittent titration technique(GITT)tests show that Ni33Mn60 has reversible structure evolution and fast Na^(+)diffusion kinetics due to the ion effect and unique P2/O3 biphasic structure,respectively.This work provides a new thought about adjusting matrix ratio for the preparation of P2/O3 biphasic cathode materials for advanced SIBs.
基金supported by the National Natural Science Foundation of China(20773090,20803049)Specialized Research Fund for the Doctoral Program of Higher Education,China(20070610026)~~
