Exploring the Enhanced Zinc Storage Performance of α-MnSe Polyhedral Microspheres and H⁺/Zn²⁺ Co-Insertion Mechanism

The newly emerged Mn-based selenides as cathodes for aqueous Zn-ion batteries (ZIBs) have drawn researchers' interest because of their lower electronegativity and better electronic conductivity compared with the corresponding Mn-based oxides. Nevertheless, the energy storage mechanism of Mn-based selenides still needs to be further clarified. Herein, the MnSe/Se and MnSe polyhedral microspheres are reported as cathodes for ZIBs, and the MnSe cathode achieves significantly enhanced specific capacity, rate performance, and cycling stability. In-depth kinetic analysis confirms that the MnSe cathode presents better kinetic behavior and density functional theory (DFT) calculations verify the fast diffusion kinetics of the MnSe cathode. More importantly, systematic ex situ characterizations reveal that the microstructured MnSe can exist stably during the charge-discharge process and store energy with H⁺/Zn²⁺ co-insertion mechanism, which is greatly different from the phase transformation of the nanostructured α-MnSe reported in the literature. Additionally, it is verified that the different types of separators exhibit remarkably different zinc storage performance of the MnSe cathode. This study not only offers a good guidance for developing high-performance ZIBs Mn-based cathode materials and explores the effect of separators on the zinc storage performance, but also provides new insights into the energy storage mechanism of the MnSe cathode.