Weakening the Space Charge Layer Effect Through Tethered Anion Electrolyte and Piezoelectric Effect Toward Ultra‐Stable Zinc Anode

The space charge layer (SCL) dilemma, caused by mobile anion concentration gradient and the rapid consumption of cations, is the fundamental reason for the generation of zinc dendrites, especially under high-rate discharge conditions. To address the issue, a physical (PbTiO₃)/chemical (AMPS-Zn) barrier is designed to construct stable zinc ion flow and disrupt the gradient of anion concentration by coupling the ferroelectric effect with tethered anion electrolyte. The ferroelectric materials PbTiO₃ with extreme-high piezoelectric constant can spontaneously generate an internal electric field to accelerate the movement of zinc ions, and the polyanionic polymer AMPS-Zn can repel mobile anions and disrupt the anions concentration gradient by tethering anions. Through numerical simulations and analyses, it is discovered that a high Zn²⁺ transference number can effectively weaken the SCL, thus suppressing the occurrence of zinc dendrites and parasitic side reactions. Consequently, an asymmetric cell using the PbTiO₃@Zn demonstrates a reversible plating/stripping performance for 2900 h, and an asymmetric cell reaches a state-of-the-art runtime of 3450 h with a high average Coulombic efficiency of 99.98%. Furthermore, the PbTiO₃@Zn/I₂ battery demonstrated an impressive capacity retention rate of 84.0% over 65000 cycles by employing a slender Zn anode.