Crystal Facet and Architecture Engineering of Metal Oxide Nanonetwork Anodes for High-Performance Potassium Ion Batteries and Hybrid Capacitors

Metal oxides are considered as prospective dual-functional anode candidates for potassium ion batteries (PIBs) and hybrid capacitors (PIHCs) because of their abundance and high theoretic gravimetric capacity; however, due to the inherent insulating property of wide band gaps and deficient ion-transport kinetics, metal oxide anodes exhibit poor K+ electrochemical performance. In this work, we report crystal facet and architecture engineering of metal oxides to achieve significantly enhanced K+ storage performance. A bismuth antimonate (BiSbO4) nanonetwork with an architecture of perpendicularly crossed single crystal nanorods of majorly exposed (001) planes are synthesized via CTAB-mediated growth. (001) is found to be the preferential surface diffusion path for superior adsorption and K+ transport, and in addition, the interconnected nanorods gives rise to a robust matrix to enhance electrical conductivity and ion transport, as well as buffering dramatic volume change during insertion/extraction of K+. Thanks to the synergistic effect of facet and structural engineering of BiSbO4 electrodes, a stable dual conversion-alloying mechanism based on reversible six-electron transfer per formula unit of ternary metal oxides is realized, proceeding by reversible coexistence of potassium peroxide conversion reactions (KO2 <-> K2O) and BixSby alloying reactions (BiSb <-> KBiSb <-> K3BiSb). As a result, BiSbO4 nanonetwork anodes show outstanding potassium ion storage in terms of capacity, cycling life, and rate capability. Finally, the implementation of a BiSbO4 nanonetwork anode in the state-of-the-art full cell configuration of both PIBs and PIHCs shows satisfactory performance in a Ragone plot that sheds light on their practical applications for a wide range of K+-based energy storage devices. We believe this study will propose a promising avenue to design advanced hierarchical nanostructures of ternary or binary conversion-type materials for PIBs, PIHCs, or even for extensive energy storage.

Automated summary

Metal oxide anodes have poor electrochemical performance in potassium ion batteries due to their wide band gaps and deficient ion-transport kinetics. In this study, crystal facet and architecture engineering of metal oxides are used to enhance the potassium ion storage performance. The nanonetwork anodes of bismuth antimonate show outstanding capacity, cycling life, and rate capability. This study proposes a promising avenue to design advanced hierarchical nanostructures for potassium ion batteries and hybrid capacitors.