高倍率长寿命P2型钠离子电池正极材料OA
High-rate and long-cycling P2-type cathode material for sodium-ion batteries
钠离子电池在启动电源、储能调频等功率型应用中潜力显著,其发展亟需兼具高倍率性能和长循环稳定性的正极材料.传统P2-Na0.67Ni0.33Mn0.67O2材料虽具有高能量密度优势,但在高电压下会出现结构退化,影响其作为功率型电源的长期可靠性.在此,本研究采用多元素掺杂的策略,设计了P2-Na0.67Zn0.05Ni0.23Fe0.1Mn0.57Ti0.05O2正极材料.该材料通过抑制高电压相变,提升了结构稳定性,在3C高倍率下循环300次后仍具有85%以上的容量保持率,展现出优异的倍率和循环性能,为功率型钠离子电池正极的设计提供了思路.
Cathode materials play a critical role in determining the energy density,cycle life,and cost-effectiveness of sodium-ion batteries(SIBs).Among various candidates,P2-type layered oxide cathodes exhibit superior high-rate charge/discharge performance due to their open Na+diffusion channels,making them particularly suitable for applications requiring rapid power delivery,such as starter batteries and grid frequency regulation.However,while the conventional P2-type Na0.67Ni0.33Mn0.67O2(P2-NNMO)cathode demonstrates high energy density,the strong O2--O2-electrostatic repulsion within the transition metal layer during high-voltage charging induces an irreversible P2 → O2 phase transition accompanied by approximately 20%volume strain.This results in severe lattice distortion and structural collapse.Additionally,oxygen oxidation at high voltages contributes to charge compensation,reducing electrochemical reaction reversibility and accelerating structural degradation.Consequently,the P2-NNMO cathode suffers from rapid capacity decay and poor cycling stability,hindering its practical application.To overcome these challenges,we developed a multi-element doping strategy to design a P2-Na0.67Zn0.05Ni0.23Fe0.1Mn0.57Ti0.05O2(P2-NZNFMTO)layered oxide cathode.The synergistic doping of Zn2+,Ti4+,and Fe3+enables concurrent optimization of structural and electrochemical properties.Specifically,Zn2+doping enhances the O2--Na+-O2-electrostatic interaction,promoting the formation of local"Na+pillars"within the Na layer to mitigate volume variation and phase transitions during cycling.Ti4+doping disrupts Na+/vacancy ordering,significantly improving Na+diffusion kinetics.The incorporation of Zn2+,Ti4+,and Fe3+also alleviates the Jahn-Teller distortion associated with Ni2+/Ni3+,enhancing cycling performance while reducing material costs.The P2-NZNFMTO cathode exhibits exceptional electrochemical performance,demonstrating 96.7%capacity retention after 100 cycles at 1C rate with a high cut-off voltage of 4.3 V.Even at a high rate of 3C,it maintains over 85%capacity retention after 300 cycles.In-situ X-ray diffraction(XRD)and galvanostatic intermittent titration technique(GITT)analyses confirm its excellent structural stability and rapid Na+transport capability at high voltages.This multi-element synergistic doping strategy establishes a novel design principle and theoretical foundation for developing high-voltage,long-cycle-life,and high-power SIB cathodes.
李培才;王绪斌;张庆华;王伯文;容晓晖;胡勇胜;李忠涛
中国石油大学(华东)化学化工学院,重质油全国重点实验室,山东 青岛 266580||中国科学院物理研究所,北京 100190中国科学院物理研究所,北京 100190||中国科学院大学材料与光电技术学院,北京 100049中国科学院物理研究所,北京 100190中国科学院物理研究所,北京 100190||中国科学院大学材料与光电技术学院,北京 100049中国科学院物理研究所,北京 100190||中国科学院大学材料与光电技术学院,北京 100049||长三角物理研究中心有限公司,江苏 溧阳 213300中国科学院物理研究所,北京 100190||中国科学院大学材料与光电技术学院,北京 100049||长三角物理研究中心有限公司,江苏 溧阳 213300||中国科学院物理研究所怀柔分部,北京 101400中国石油大学(华东)化学化工学院,重质油全国重点实验室,山东 青岛 266580
化学化工
钠离子电池高倍率多元素掺杂正极材料高电压
Sodium-ion batteryHigh rateMulti-element dopingCathode materialsHigh-voltage
《物理化学学报》 2026 (5)
140-151,12
国家重点研发规划(2022YFB2402500)国家自然科学基金(52394170,52394174,92372116和22422906)北京市自然科学基金(JQ24006)和中国科协青年人才托举工程(2022QNRC001)资助项目.
评论