Layered P2-type cathodes with high voltage,large capacity,and easy synthesis show great potential for developing sodium(Na)-ion batteries(NIBs).However,the P2–O2 phase transition makes their structural degradation an...Layered P2-type cathodes with high voltage,large capacity,and easy synthesis show great potential for developing sodium(Na)-ion batteries(NIBs).However,the P2–O2 phase transition makes their structural degradation and the Na^(+)/vacancy ordering lowers their redox kinetics.Here,we rationally propose a compositionally graded P2-type cathode,where nickel(Ni)and manganese(Mn)fractions decrease gradually,and cobalt(Co)content increases contiguously from the inside to the outside of a secondary particle.Inside these particles,the Ni/Mn-based compound delivers high capacity and high voltage.On the surface of particles,the Co/Mn-based solid solution offers a stable buffer matrix.Benefiting from these synergistic effects,this graded P2-type cathode shows the elimination of P2–O2 transformation even when charged to 4.4 V,which enables good structural stability,maintaining capacity retention reaching~80%within 300 cycles.Moreover,the Na^(+)/vacancy ordering superstructure is further suppressed,and the Na^(+)diffusion kinetics is significantly improved.The proposed graded structure with optimized chemical composition offers a new perspective for eliminating the unwanted phase transition and thus enhancing the electrochemistry of high-voltage layered cathodes for advanced NIBs.展开更多
基金funded by the National Natural Science Foundation of China(No.52102252)the Natural Science Foundation of Shandong Province(No.ZR2021QB052)China Postdoctoral Science Foundation(No.2021T140268).
文摘Layered P2-type cathodes with high voltage,large capacity,and easy synthesis show great potential for developing sodium(Na)-ion batteries(NIBs).However,the P2–O2 phase transition makes their structural degradation and the Na^(+)/vacancy ordering lowers their redox kinetics.Here,we rationally propose a compositionally graded P2-type cathode,where nickel(Ni)and manganese(Mn)fractions decrease gradually,and cobalt(Co)content increases contiguously from the inside to the outside of a secondary particle.Inside these particles,the Ni/Mn-based compound delivers high capacity and high voltage.On the surface of particles,the Co/Mn-based solid solution offers a stable buffer matrix.Benefiting from these synergistic effects,this graded P2-type cathode shows the elimination of P2–O2 transformation even when charged to 4.4 V,which enables good structural stability,maintaining capacity retention reaching~80%within 300 cycles.Moreover,the Na^(+)/vacancy ordering superstructure is further suppressed,and the Na^(+)diffusion kinetics is significantly improved.The proposed graded structure with optimized chemical composition offers a new perspective for eliminating the unwanted phase transition and thus enhancing the electrochemistry of high-voltage layered cathodes for advanced NIBs.
