Eco-friendly synthesis of hierarchical heterostructured CsV3O8/V2O5 composite cathode: lattice stabilization and vanadium dissolution resistance for long-life aqueous zinc-ion batteries
摘要
Developing durable and high-capacity cathode materials is key to advancing aqueous zinc-ion batteries (ZIBs). Herein, we report a previously unreported hierarchical heterostructured CsV3O8/V2O5 composite (HH–CsVO/VO) cathode synthesized via a simple, eco-friendly and low energy ambient-temperature stirring method that avoids toxic solvents and high-temperature treatments. The incorporation of Cs+ ions into the VO framework induces significant lattice compression, compressive strain, and new V coordination environments, leading to mixed-valence V states (V5+/V4+/V3+), as confirmed by solid-state 51V nuclear magnetic resonance (NMR) spectroscopy and ex-situ X-ray photoelectron spectroscopy (XPS) analyses. This structural modulation is accompanied by band gap narrowing (2.71 → 2.19 eV) and a reduced work function (5.00 → 4.14 eV), enhancing redox kinetics and Zn²⁺ intercalation pathways. Raman and Fourier-transform infrared spectroscopy analyses reveal Cs-induced lattice distortion and compressive strain, while ultraviolet photoelectron spectroscopy confirms interfacial electronic modulation. Ex-situ X-ray diffraction and XPS demonstrate highly reversible phase evolution and structural stability during cycling. The HH–CsVO/VO electrode delivers a high reversible capacity of 482.7 mAh g− 1 after 200 cycles at 0.3 A g− 1 and maintains 240.63 mAh g− 1 after 3000 cycles at 3 A g− 1, outperforming pristine VO. Notably, the composite exhibits suppressed voltage polarization and significantly reduced V dissolution, supported by immersion tests and stable cycling. Although Cs–O bonding is not vibrationally active, it is proposed to stabilize vanadyl surface groups and limit dissolution. This work highlights how interfacial engineering and electronic modulation, achieved through green chemistry, can enable high-performance aqueous ZIB cathodes.