High Flux and Stability of Cationic Intercalation in Transition-Metal Oxides: Unleashing the Potential of Mn t2g Orbital via Enhanced π-Donation

Transition-metal oxides (TMOs) often struggle with challenges related to low electronic conductivity and unsatisfactory cyclic stability toward cationic intercalation. In this work, we tackle these issues by exploring an innovative strategy: leveraging heightened π-donation to activate the t_2g orbital, thereby enhancing both electron/ion conductivity and structural stability of TMOs. We engineered Ni-doped layered manganese dioxide (Ni-MnO₂), which is characterized by a distinctive Ni-O-Mn bridging configuration. Remarkably, Ni-MnO₂ presents an impressive capacitance of 317 F g^-1 and exhibits a robust cyclic stability, maintaining 81.58% of its original capacity even after 20,000 cycles. Mechanism investigations reveal that the incorporation of Ni-O-Mn configurations stimulates a heightened π-donation effect, which is beneficial to the π-type orbital hybridization involving the O 2p and the t_2g orbital of Mn, thereby accelerating charge-transfer kinetics and activating the redox capacity of the t_2g orbital. Additionally, the charge redistribution from Ni to the t_2g orbital of Mn effectively elevates the low-energy orbital level of Mn, thus mitigating the undesirable Jahn-Teller distortion. This results in a subsequent decrease in the electron occupancy of the π*-antibonding orbital, which promotes an overall enhancement in structural stability. Our findings pave the way for an innovative paradigm in the development of fast and stable electrode materials for intercalation energy storage by activating the low orbitals of the TM center from a molecular orbital perspective.