In Operando X-ray Studies of High-Performance Lithium-Ion Storage in Keplerate-Type Polyoxometalate Anodes.

Polyoxometalates (POMs) have emerged as potential anode materials for lithium-ion batteries (LIBs) owing to their ability to transfer multiple electrons. Although POM anode materials exhibit notable results in LIBs, their energy-storage mechanisms have not been well-investigated. Here, we utilize various in operando and ex situ techniques to verify the charge-storage mechanisms of a Keplerate-type POM Na2K23{[(MoVI)MoVI5O21(H2O)3(KSO4)]12 [(VIVO)30(H2O)20(SO4)0.5]}·ca200H2O ({Mo72V30}) anode in LIBs. The {Mo72V30} anode provides a high reversible capacity of up to ∼1300 mA h g-1 without capacity fading for up to 100 cycles. The lithium-ion storage mechanism was studied systematically through in operando synchrotron X-ray absorption near-edge structure, ex situ X-ray diffraction, ex situ extended X-ray absorption fine structure, ex situ transmission electron microscopy, in operando synchrotron transmission X-ray microscopy, and in operando Raman spectroscopy. Based on the abovementioned results, we propose that the open hollow-ball structure of the {Mo72V30} molecular cluster serves as an electron/ion sponge that can store a large number of lithium ions and electrons reversibly via multiple and reversible redox reactions (Mo6+ ↔ Mo1+ and V5+/V4+↔ V1+) with fast lithium diffusion kinetics (DLi+: 10-9-10-10 cm2 s-1). No obvious volumetric expansion of the microsized {Mo72V30} particle is observed during the lithiation/delithiation process, which leads to high cycling stability. This study provides comprehensive analytical methods for understanding the lithium-ion storage mechanism of such complicated POMs, which is important for further studies of POM electrodes in energy-storage applications.