High-energy O3-Na1-2xCax[Ni0.5Mn0.5]O2 cathode for long-life sodium-ion batteries
To facilitate the practical realization of sodium-ion batteries, the energy density, determined by the output operating volt-age and/or capacity, needs to be improved to the level of commercial Li-ion batteries. Herein, the O3-type Na0.98Ca0.01[Ni0.5Mn0.5]O2 is synthesized by incorporating Ca2+ into the NaO6 octahedron of Na[Ni0.5Mn0.5]O2 and its potential use as a cathode material for high energy density SIBs is demonstrated. The ionic radius of calcium (≈1.00 Å) is similar to that of sodium (≈1.02 Å); hence, it is energetically favorable for calcium to occupy sites in the sodium layers. At a wide operating voltage range of 2.0-4.3 V, O3-type Na0.98Ca0.01[Ni0.5Mn0.5]O2 exhibits a reversible O3-P3-O3 phase transition with small volume changes compared to Ca-free Na[Ni0.5Mn0.5]O2 because of the strong interaction between Ca2+ with O2- and delivers a high reversible capacity of 209 mAh g-1 at 15 mA g-1 with improved cycling stability. Moreover, Ca substitution improves the practically useful aspects such as thermal and air stability. The prototype pouch full cell with a hard carbon anode maintains an excellent capacity retention of 67 % over 300 cycles. Thus, this study provides an efficient and simple method to boost the performance and applicability of layered oxide cathode materials for practical applications.