03-type layered metal oxides hold great promise for sodium-ion batteries cathodes owing to their energy density advantage.However,the severe irreversible phase transition and sluggish Na^(+)diffusion kinetics pose sig...03-type layered metal oxides hold great promise for sodium-ion batteries cathodes owing to their energy density advantage.However,the severe irreversible phase transition and sluggish Na^(+)diffusion kinetics pose significant challenges to achieve high-performance layered cathodes.Herein,a boron-doped03-type high entropy oxide Na(Fe_(0.2)Co_(0.15)Cu_(0.05)Ni_(0.2)Mn_(0.2)Ti_(0.2))B_(0.02)O_(2)(NFCCNMT-B_(0.02))is designed and the covalent B-O bonds with high entropy configuration ensure a robust layered structure.The obtained cathode NFCCNMT-B_(0.02)exhibits impressive cycling performance(capacity retention of 95%and 82%after100 cycles and 300 cycles at 1 and 10 C,respectively)and outstanding rate capability(capacity of 83 mAh g^(-1)at 10 C).Furthermore,the NFCCNMT-B_(0.02)demonstrates a superior wide-temperature performance,maintaining the same capacity level(113,4 mAh g^(-1)@-20℃,121 mAh g^(-1)@25℃,and 119 mAh g^(-1)@60℃)and superior cycle stability(90%capacity retention after 100 cycles at 1 C at-20℃).The high-entropy configuration design with boron doping strategy contributes to the excellent sodium-ion storage performance.The high-entropy configuration design effectively suppresses irreversible phase transitions accompanied by small volume changes(ΔV=0.65 A3).B ions doping expands the Na layer distance and enlarges the P3 phase region,thereby enhancing Na^(+)diffusion kinetics.This work offers valuable insights into design of high-performance layered cathodes for sodium-ion batteries operating across a wide temperature.展开更多
Combining in-depth neutron diffraction and systematic bulk studies,we discover that the√5×√5 Fe vacancy order,with its associated block antiferromagnetic order,is the ground state with varying occupancy ratios ...Combining in-depth neutron diffraction and systematic bulk studies,we discover that the√5×√5 Fe vacancy order,with its associated block antiferromagnetic order,is the ground state with varying occupancy ratios of the iron 16i and vacancy 4d sites across the phase-diagram of K_(x)Fe_(2)-ySe_(2).The orthorhombic order,with one of the four Fe sites vacant,appears only at intermediate temperatures as a competing phase.The material experiences an insulator to metal crossover when the√5×√5 order is highly developed.Superconductivity occurs in such a metallic phase.展开更多
基金financially supported by the National Natural Science Foundation of China(No.52071073,52177208,and52171202)Hebei Province“333 talent project”(No.C20221012)+1 种基金the Science and Technology Project of Hebei Education Department(BJK2023005)Hebei Province Graduate Innovation Funding Program CXZZBS2024177。
文摘03-type layered metal oxides hold great promise for sodium-ion batteries cathodes owing to their energy density advantage.However,the severe irreversible phase transition and sluggish Na^(+)diffusion kinetics pose significant challenges to achieve high-performance layered cathodes.Herein,a boron-doped03-type high entropy oxide Na(Fe_(0.2)Co_(0.15)Cu_(0.05)Ni_(0.2)Mn_(0.2)Ti_(0.2))B_(0.02)O_(2)(NFCCNMT-B_(0.02))is designed and the covalent B-O bonds with high entropy configuration ensure a robust layered structure.The obtained cathode NFCCNMT-B_(0.02)exhibits impressive cycling performance(capacity retention of 95%and 82%after100 cycles and 300 cycles at 1 and 10 C,respectively)and outstanding rate capability(capacity of 83 mAh g^(-1)at 10 C).Furthermore,the NFCCNMT-B_(0.02)demonstrates a superior wide-temperature performance,maintaining the same capacity level(113,4 mAh g^(-1)@-20℃,121 mAh g^(-1)@25℃,and 119 mAh g^(-1)@60℃)and superior cycle stability(90%capacity retention after 100 cycles at 1 C at-20℃).The high-entropy configuration design with boron doping strategy contributes to the excellent sodium-ion storage performance.The high-entropy configuration design effectively suppresses irreversible phase transitions accompanied by small volume changes(ΔV=0.65 A3).B ions doping expands the Na layer distance and enlarges the P3 phase region,thereby enhancing Na^(+)diffusion kinetics.This work offers valuable insights into design of high-performance layered cathodes for sodium-ion batteries operating across a wide temperature.
基金Supported by the National Basic Research Program of China under Grant Nos 2012CB921700,2011CBA00112,2011CBA00103 and 2009CB929104National Natural Science Foundation of China under Grant Nos 11034012,11190024,10974175 and 10934005.
文摘Combining in-depth neutron diffraction and systematic bulk studies,we discover that the√5×√5 Fe vacancy order,with its associated block antiferromagnetic order,is the ground state with varying occupancy ratios of the iron 16i and vacancy 4d sites across the phase-diagram of K_(x)Fe_(2)-ySe_(2).The orthorhombic order,with one of the four Fe sites vacant,appears only at intermediate temperatures as a competing phase.The material experiences an insulator to metal crossover when the√5×√5 order is highly developed.Superconductivity occurs in such a metallic phase.
