Chemomechanical Design Factors for High Performance in Manganese-Based Spinel Cathode Materials for Advanced Sodium-Ion Batteries.

Manganese-based spinel cathode materials for sodium-ion batteries (SIBs) are promising candidates for next-generation batteries; especially, Na[Ni0.5Mn1.5]O4 (NNMO) should get attention because of its relatively high operating voltage and firm octahedral host structure. Here, first-principles calculations and the phase field method are used to elucidate the reasons for the low performance of NNMO compared with Li[Ni0.5Mn1.5]O4, and we determine the requirements for realizing high-performance cathode materials for SIBs. Owing to the Ni2+/Ni4+ double redox, NNMO could operate at a high voltage; however, the large Na+ increases the local site energy of the redox center, promoting electron extraction from the redox center, leading to unexpected voltage loss. Additionally, the homogeneous free energy confirms that NNMO would undergo phase separation into fully intercalated and deintercalated phases, inducing lattice misfits along the interfaces of the two phases. Particularly, a higher phase transition barrier and large Na+ cause fast phase separation, inducing increased polarization and severe stress field upon cycling. The present analysis with comprehensive first-principles calculations and the phase field method provides three critical factors toward high electrochemical performance: (i) strengthening Ni-O bonding to avoid undesirable voltage loss, (ii) increasing the vacancy/Na solubility during (de)sodiation to enhance cyclability, and (iii) suppressing the structural distortion during (de)sodiation to prevent mechanical failure. Based on these crucial points, additionally, we suggest the M-pillared Na1-xMx[Ni0.5Mn1.5]O4 (monovalent or divalent species, M), where the M works to strengthen the redox center for improved energy density and to alleviate the drastic structural change and voltage hysteresis for better cyclability, would have superior electrochemical performance as a cathode material for SIBs.