Synergistic Piezoelectric‐Field and Crystal Plane Manipulation in Composite Solid Electrolytes Toward High‐Rate Zinc Metal Batteries

ABSTRACT Rechargeable zinc‐ion batteries are promising for large‐scale storage, yet persistent dendrite growth and interfacial side reactions at the Zn anode compromise the cycling stability and rate capability. The solidification of electrolytes offers a viable approach to addressing these issues, but is often hindered by insufficient salt dissociation, sluggish Zn 2+ transport, and unstable Zn‐electrolyte interfaces. Herein, a piezoelectric‐field‐coupled composite solid electrolyte is developed by integrating ZnO into the poly(vinylidene fluoride‐hexafluoropropylene) matrix. ZnO synergistically triggers electroactive β‐phase enrichment and amplifies polarization, establishing a persistent interfacial electric field. This field‐driven regulation facilitates salt dissociation and accelerates Zn 2+ transport while homogenizing interfacial flux to lower nucleation overpotential and steer Zn deposition toward the thermodynamically stable Zn(002) plane. Simultaneously, the stabilized interface promotes the formation of a thin, continuous solid electrolyte interphase rich in inorganic ZnF 2 /ZnS inner layer, which further passivates the anode against parasitic reactions. Consequently, Zn|Zn symmetric cell displays an exceptional lifespan of 2750 h at 0.1 mA cm −2 , with ultra‐high critical current density of 7.0 mA cm −2 . This work underscores the efficacy of piezoelectric polarization in coupling deposition crystallography with interfacial chemistry, establishing a field‐engineered structure‐function integrated design paradigm for high‐performance, durable solid‐state metal batteries.