High-Capacity and Self-Stabilized Manganese Carbonate Microspheres as Anode Material for Lithium-Ion Batteries.

Manganese carbonate (MnCO3) is an attractive anode material with high capacity based on conversion reaction for lithium-ion batteries (LIBs), but its application is mainly hindered by poor cycling performance. Building nanostructures/porous structures and nanocomposites has been demonstrated as an effective strategy to buffer the volume changes and maintain the electrode integrity for long-term cycling. It is widely believed that microsized MnCO3 is not suitable for use as anode material for LIBs because of its poor conductivity and the absence of nanostructure. Herein, different from previous reports, spherical MnCO3 with the mean diameters of 6.9 μm (MnCO3-B), 4.0 μm (MnCO3-M), and 2.6 μm (MnCO3-S) were prepared via controllable precipitation and utilized as anode materials for LIBs. It is interesting that the as-prepared MnCO3 microspheres demonstrate both high capacity and excellent cycling performance comparable to their reported nanosized counterparts. MnCO3-B, MnCO3-M, and MnCO3-S deliver reversible specific capacities of 487.3, 573.9, and 656.8 mA h g(-1) after 100 cycles, respectively. All the MnCO3 microspheres show capacity retention more than 90% after the initial stage. The advantages of MnCO3 microspheres were investigated via constant-current charge/discharge, cyclic voltammetry and electrochemical impedance spectroscopy. The results indicate that there should be substantial structure transformation from microsized particle to self-stabilized nanostructured matrix for MnCO3 at the initial charge/discharge stage. The evolution of EIS during charge/discharge clearly indicates the formation and stabilization of the nanostructured matrix. The self-stabilized porous matrix maintains the electrode structure to deliver excellent cycling performance, and contributes extra capacity beyond conversion reaction.