Ternary Ni/Mn/Cu cations pre-intercalation to realize high-rate vanadium pentoxide hydrate cathode for aqueous zinc-ion batteries
摘要
Layered V2O5·H2O (vanadium pentoxide hydrate) is a highly promising cathode material for aqueous zinc-ion batteries owing to its large interlayer space, variable V valence states, and unique interlayer H2O. However, the low electronic conductivity and easily exfoliated lattice layers lead to its poor charge transport kinetics and lattice stability. In this regard, we develop a ternary transition metal ions pre-intercalation strategy, where ternary Ni/Mn/Cu cations are successfully pre-intercalated into V2O5·H2O by one-step hydrothermal method. It is revealed that Mn cation activates the additional Mn4+/Mn3+ redox reaction, and ternary Ni/Mn/Cu cations cause the strong ion column effect, induce the highest p-band center of O, and improve the electrical conductivity, thus simultaneously enhancing the lattice stability and charge transport kinetics. As a result, the energy density of 391 Wh kg−1 at 0.1 A g−1 and the high-rate capability with a capacity of 240 mAh g−1 at 3 A g−1 after 600 cycles are achieved. Besides, the electrochemical reaction mechanism is revealed to be H+ intercalation at high potentials, and followed Zn2+ intercalation at low potentials, and Zn2+ intercalation contributes most of the capacity (> 65%) and H+ intercalation promotes the optimization of electrochemical performance.
Graphical abstract