Size-Dependent Reaction Mechanism of λ -MnO 2 Particles as Cathodes in Aqueous Zinc-Ion Batteries

Abstract

Manganese dioxide (MnO 2 ) with different crystal structures has been widely investigated as the cathode material for Zn-ion batteries, among which spinel λ -MnO 2 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 -MnO 2 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 -MnO 2 particles (MPs, ~0.9  μ m) unexpectedly undergo an activation process with the capacity continuously increasing over the first 50 cycles, which can be attributed to the formation of amorphous MnO x nanosheets in the open interstitial space of the MP electrode. By adding MnSO 4 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.