Manganese dioxide (MnO2) with different crystal structures has been widely investigated as the cathode material for Zn-ion batteries, among which spinel λ-MnO2 is yet rarely reported because Zn-ion intercalation in spinel lattice is speculated to be limited by the narrow three-dimensional tunnels. In this work, we demonstrate that Zn-ion insertion in spinel lattice can be enhanced by reducing particle size and elucidate an intriguing electrochemical reaction mechanism dependent on particle size. Specifically, λ-MnO2 nanoparticles (NPs, ~80 nm) deliver a high capacity of 250 mAh/g at 20 mA/g due to large surface area and solid-solution type phase transition pathway. Meanwhile, severe water-induced Mn dissolution leads to the poor cycling stability of NPs. In contrast, micron-sized λ-MnO2 particles (MPs, ~0.9 μm) unexpectedly undergo an activation process with the capacity continuously increasing over the first 50 cycles, which can be attributed to the formation of amorphous MnOx nanosheets in the open interstitial space of the MP electrode. By adding MnSO4 to the electrolyte, Mn dissolution can be suppressed, leading to significant improvement in the cycling performance of NPs, with a capacity of 115 mAh/g retained at 1 A/g for over 500 cycles. This work pinpoints the distinctive impacts of the particle size on the reaction mechanism and cathode performance in aqueous Zn-ion batteries.
ASJC Scopus subject areas
- Energy (miscellaneous)
- Fuel Technology
- Renewable Energy, Sustainability and the Environment
- Materials Science (miscellaneous)