Self‐Assembly of Polyoxometalate‐Resorcin[4]arene‐Based Inorganic‐Organic Complexes: Metal Ion Effects on the Electrochemical Performance of Lithium Ion Batteries

Abstract With their adjustable structures and diverse functions, polyoxometalate (POM)‐resorcin[4]arene‐based inorganic–organic complexes are a kind of potential multifunctional material. They have potential applications for lithium ion batteries (LIBs). However, the relationship between different coordinated metal ions and electrochemical performance has rarely been investigated. Here, three functionalized POM‐resorcin[4]arene‐based inorganic–organic materials, [Co 2 (TMR4 A) 2 (H 2 O) 10 ][SiW 12 O 40 ] ⋅ 2 EtOH ⋅ 4.5 H 2 O ( 1 ), [Ni 2 (TMR4 A) 2 (H 2 O) 10 ][SiW 12 O 40 ] ⋅ 4 EtOH ⋅ 13 H 2 O ( 2 ), and [Zn 2 (TMR4 A) 2 (H 2 O) 10 ][SiW 12 O 40 ] ⋅ 2 EtOH ⋅ 2 H 2 O ( 3 ), have been synthesized. Furthermore, to enhance the conductivities of these compounds, 1–3 were doped with reduced graphene oxide (RGO) to give composites 1 @RGO‐ 3 @RGO, respectively. As anode materials for LIBs, 1 @RGO‐ 3 @RGO can deliver very high discharge capacities (1445.9, 1285.0 and 1095.3 mAh g −1 , respectively) in the initial run, and show discharge capacities of 898, 665 and 651 mAh g −1 , respectively, at a current density of 0.1 A g −1 over 100 runs. More importantly, the discharge capacities of 319, 283 and 329 mAh g −1 were maintained for 1 @RGO‐ 3 @RGO even after 400 cycles at large current density (1 A g −1 ).