Regulating Zn2+ Migration‐Diffusion Behavior by Spontaneous Cascade Optimization Strategy for Long‐Life and Low N/P Ratio Zinc Ion Batteries

Abstract Parasitic side reactions and dendrite growth on zinc anodes are formidable issues causing limited lifetime of aqueous zinc ion batteries (ZIBs). Herein, a spontaneous cascade optimization strategy is first proposed to regulate Zn 2+ migration‐diffusion behavior. Specifically, PAPE@Zn layer with separation‐reconstruction properties is constructed in situ on Zn anode. In this layer, well‐soluble poly(ethylene oxide) (PEO) can spontaneously separation to bulk electrolyte and weaken the preferential coordination between H 2 O and Zn 2+ to achieve primary optimization. Meanwhile, poor‐soluble polymerized‐4‐acryloylmorpholine (PACMO) is reconstructed on Zn anode as hydrophobic flower‐like arrays with abundant zincophilic sites, further guiding the de‐solvation and homogeneous diffusion of Zn 2+ to achieve the secondary optimization. Cascade optimization effectively regulates Zn 2+ migration‐diffusion behavior, dendrite growth and side reactions of Zn anode are negligible, and the stability is significantly improved. Consequently, symmetrical cells exhibit stability over 4000 h (1 mA cm −2 ). PAPE@Zn//NH 4 + −V 2 O 5 full cells with a high current density of 15 A g −1 maintains 72.2 % capacity retention for 12000 cycles. Even better, the full cell demonstrates excellent performance of cumulative capacity of 2.33 Ah cm −2 at ultra‐low negative/positive (N/P) ratio of 0.6 and a high mass‐loading (~17 mg cm −2 ). The spontaneous cascade optimization strategy provides novel path to achieve high‐performance and practical ZIBs.