Work

The Role of Divalent (Zn 2+ /Mg 2+ /Cu 2+ ) Substituents in Achieving Full Capacity of Sodium Layered Oxides for Na-Ion Battery Applications

Year: 2020

Type: article

Abstract: O3-type layered sodium transition metal oxides, for example, NaNi 0.5 Mn 0.5– z Ti z O 2, having one sodium per transition metal ion could be attractive positive electrode materials for achieving high energy density sodium-ion batteries, provided that we can reversibly utilize their full Na content. However, the layered structure on cycling undergoes a series of phase transitions in which the fully desodiated O1 phase shows a huge reduction in cell volume together with cation migration, both of which are detrimental for long-term cycling performance. Hence, the practical capacity of layered oxides is restricted to solely ∼0.5–0.6 Na (oxidation up to ∼4 V vs Na + /Na 0 ), avoiding the complete removal of sodium. Herein, we show that the partial substitution of a redox-active Ni 2+ cation by an inactive one (e.g., Zn 2+ to form NaNi 0.45 Zn 0.05 Mn 0.4 Ti 0.1 O 2 ) suppresses the phase transitions at high voltage (>4 V vs Na + /Na 0 ) and helps in utilizing the maximum capacity of the material (170 mAh g –1 with ∼0.8 Na) without much degradations upon long cycling. The fully charged phase (Na 0.2 Ni 0.45 Zn 0.05 Mn 0.4 Ti 0.1 O 2 ), as determined by high-resolution electron transmission microscopy, shows a P3-O1 intergrowth structure in which the O1 phase is present only locally as nanoscale domains. We believe that the formation of P3-O1 intergrowths in the Zn-substituted material, in contrast to the distinct O1 phase for unsubstituted NaNi 0.5 Mn 0.4 Ti 0.1 O 2, restricts structural degradations during cycling and improves the long-term cycling stability. Similar substitution chemistry can be extended to Cu 2+ and Mg 2+ ions as well. The NaNi 0.45 Zn 0.05 Mn 0.4 Ti 0.1 O 2 positive electrode material on implementation in 18650 Na-ion cells show electrochemical performances comparable to that of polyanionic Na 3 V 2 (PO 4 ) 2 F 3 /C cells.

Source: Chemistry of Materials

DOI: 10.1021/acs.chemmater.9b05205