ABSTRACT
To meet future energy demands, currently, dominant lithium-ion batteries (LIBs) must be supported by abundant and cost-effective alternative battery materials. Potassium-ion batteries (KIBs) are promising alternatives to LIBs because KIB materials are abundant and because KIBs exhibit intercalation chemistry like LIBs and comparable energy densities. In pursuit of superior batteries, designing and developing highly efficient electrode materials are indispensable for meeting the requirements of large-scale energy storage applications. Despite using graphite anodes in KIBs instead of in sodium-ion batteries (NIBs), developing suitable KIB cathodes is extremely challenging and has attracted considerable research attention. Among the various cathode materials, layered metal oxides have attracted considerable interest owing to their tunable stoichiometry, high specific capacity, and structural stability. Therefore, the recent progress in layered metal-oxide cathodes is comprehensively reviewed for application to KIBs and the fundamental material design, classification, phase transitions, preparation techniques, and corresponding electrochemical performance of KIBs are presented. Furthermore, the challenges and opportunities associated with developing layered oxide cathode materials are presented for practical application to KIBs.
ABSTRACT
NaCrO2 with high rate-capability is an attractive cathode material for sodium-ion batteries (NIBs). However, the amount of reversibly extractable Na+ ions is restricted by half, which results in relatively low energy density for practical NIB cathodes. Herein, we describe aliovalent-doped O3-Na0.9[Cr0.9Sn0.1]O2 (NCSnO) and O3-Na0.8[Cr0.9Sb0.1]O2 (NCSbO), both of which show high-voltage characteristics that translate to an increase in energy density. In contrast to NaCrO2, NCSnO and NCSbO can be reversibly charged to 3.80 and 3.95 V, respectively, delivering 0.5 Na+ along with Cr3+/4+ redox alone. The reversible chargeability to Na0.4[Cr0.9Sn0.1]O2 and Na0.3[Cr0.9Sb0.1]O2 is not associated with the suppression of Cr6+ formation. Both compounds show concentrations of Cr6+ that are higher than that of Na0.3CrO2, with an absence of O3' phases. This implies that aliovalent-doping contributes to a suppression of the Cr6+ migration into tetrahedral sites in the interslab space, which reduces the possibility of irreversible comproportionation. NCSnO and NCSbO deliver capacities comparable to that of NaCrO2, but show a higher average discharge voltage (2.94 V for NaCrO2; 3.14 V for NCSnO; 3.21 V for NCSbO), which leads to a noticeable increase in energy densities. The high-voltage characteristics of NCSnO and NCSbO are also validated via density-functional-theory calculations.
