Sodium-ion intercalation oxides generally possess high compositional diversity according to their different stacking sequences.The sodium diffusion pathway in layered P-type materials used in sodium-ion batteries is o...Sodium-ion intercalation oxides generally possess high compositional diversity according to their different stacking sequences.The sodium diffusion pathway in layered P-type materials used in sodium-ion batteries is open,which can increase their rate capability by directly transmitting Na+between adjacent triangular prismatic channels,rather than passing through an intermediate tetrahedral site in O-type structure.However,how the structure chemistry of the P-type oxides determines their electrochemical properties has not been fully understood yet.Herein,by comparing the crystalline structures,electrochemical behaviors,ion/electron transport dynamics of a couple of P-type intercalation cathodes,P2-Na_(2/3)Ni1/3Mn_(2/3)O_(2)and P3-Na_(2/3)Ni_(1/3)Mn_(2/3)O_(2)with the same compositions,we demonstrate experimentally and computationally that the P2 phase delivers better cycling stability and rate capability than the P3 counterpart due to the predominant contribution of the faster intrinsic Na diffusion kinetics in the P2 bulk.We also point out that it is the electronic conductivity that captures the key electrochemistry of layered P3-type materials and makes them possible to enhance the sodium storage performance.The results reveal that the correlation between stacking structure and functional properties in two typical layered P-type cathodes,providing new guidelines for preparing and designing alkali-metal layered oxide materials with improved battery performance.展开更多
基金supported by the National Natural Science Foundation of China (U1607128,52102302 and 21521005)Natural Science Foundation of Beijing (2222020)+1 种基金the Young Talent Support Plan and Siyuan Scholar of Xi’an Jiaotong University (DQ6J011 and DQ1J009)State Key Laboratory of Electrical Insulation and Power Equipment (EIPE23313)
文摘Sodium-ion intercalation oxides generally possess high compositional diversity according to their different stacking sequences.The sodium diffusion pathway in layered P-type materials used in sodium-ion batteries is open,which can increase their rate capability by directly transmitting Na+between adjacent triangular prismatic channels,rather than passing through an intermediate tetrahedral site in O-type structure.However,how the structure chemistry of the P-type oxides determines their electrochemical properties has not been fully understood yet.Herein,by comparing the crystalline structures,electrochemical behaviors,ion/electron transport dynamics of a couple of P-type intercalation cathodes,P2-Na_(2/3)Ni1/3Mn_(2/3)O_(2)and P3-Na_(2/3)Ni_(1/3)Mn_(2/3)O_(2)with the same compositions,we demonstrate experimentally and computationally that the P2 phase delivers better cycling stability and rate capability than the P3 counterpart due to the predominant contribution of the faster intrinsic Na diffusion kinetics in the P2 bulk.We also point out that it is the electronic conductivity that captures the key electrochemistry of layered P3-type materials and makes them possible to enhance the sodium storage performance.The results reveal that the correlation between stacking structure and functional properties in two typical layered P-type cathodes,providing new guidelines for preparing and designing alkali-metal layered oxide materials with improved battery performance.
