Three-in-one organic-inorganic heterostructures: From scalable ball-milling synthesis to freestanding cathodes with high areal capacity for aqueous zinc-ion batteries

Aqueous Zn-ion batteries (AZIBs) have great potential in large-scale energy storage, however, developing suitable cathodes with high energy/power densities remains highly challenging. Herein, a unique organic-inorganic heterostructures (denoted as Ov-PVO/G) of poly(3,4-ethylenedioxythiophene) intercalated V2O5 nanocrystals anchored on few-layer graphene by a simple and scalable ball-milling approach are demonstrated for high areal-capacity AZIBs cathodes, in which, adjusted interlayer spacing, abundant oxygen vacancies and robust heterointerfaces can be simultaneously constructed. Moreover, the feature of being well dispersed in different polar solvents (H2O, NMP, etc.) enable facile incorporation of the Ov-PVO/G heterostructures into conductive networks of single-walled carbon nanotubes to fabricate freestanding composite cathodes. Electrochemical measurement and first-principles calculations indicate that such “Three-in-One” heterostructure can significantly enhance Zn2+ adsorption/desorption, electrical conductivity and charge transfer due to strong synergy, thereby exhibiting high-capacity and accelerated reaction kinetics during cycling. Specifically, at a practical mass loading of 12.0 mg/cm2, the freestanding Ov-PVO/G cathodes show a high areal-capacity of 6.1 mAh/cm2 at 2.4 mA/cm2 and works stable with an area-capacity of 1.63 mAh/cm2 at 120 mA/cm2 after 500 cycles. More importantly, flexible soft-packaged AZIBs based on 3×3 cm2 high mass-loading Ov-PVO/G cathodes deliver record-high and stable electric energy beyond 21.5 mAh at different bending states. This work paves a more promising way to practical application of high-performance AZIBs.