Polypyrrole pre-intercalation engineering-induced NH4+ removal in tunnel ammonium vanadate toward high-performance zinc ion batteries

Ammonium vanadate with stable bi-layered structure and superior mass-specific capacity have emerged as competitive cathode materials for aqueous rechargeable zinc-ion batteries (AZIBs). Nevertheless, fragile N H…O bonds and too strong electrostatic interaction by virtue of excessive NH 4 + will lead to sluggish Zn 2+ ion mobility, further largely affects the electro-chemical performance of ammonium vanadate in AZIBs. The present work incorporates polypyrrole (PPy) to partially replace NH 4 + in NH 4 V 4 O 10 (NVO), resulting in the significantly enlarged interlayers (from 10.1 to 11.9 Å), remarkable electronic conductivity, increased oxygen vacancies and reinforced layered structure. The partial removal of NH 4 + will alleviate the irreversible deammoniation to protect the laminate structures from collapse during ion insertion/extraction. The expanded interlayer spacing and the increased oxygen vacancies by the virtue of the introduction of polypyrrole improve the ionic diffusion, enabling exceptional rate performance of NH 4 V 4 O 10 . As expected, the resulting polypyrrole intercalated ammonium vanadate (NVOY) presents a superior discharge capacity of 431.9 mAh g −1 at 0.5 A g −1 and remarkable cycling stability of 219.1 mAh g −1 at 20 A g −1 with 78 % capacity retention after 1500 cycles. The in-situ electrochemical impedance spectroscopy (EIS), in-situ X-ray diffraction (XRD), ex-situ X-ray photoelectron spectroscopy (XPS) and ex-situ high resolution transmission electron microscopy (HR-TEM) analysis investigate a highly reversible intercalation Zn-storage mechanism, and the enhanced the redox kinetics are related to the combined effect of interlayer regulation, high electronic conductivity and oxygen defect engineering by partial substitution NH 4 + of PPy incorporation.