Abstract
The inner Helmholtz plane and thus derived solid-electrolyte interphase (SEI) are crucial interfacial structure to determine the electrochemical stability of Zn-ion battery (ZIB). In this work, we demonstrate that introducing β-cyclodextrins (CD) as anion-receptors into Zn(OTf)2 aqueous electrolyte could significantly optimize the Zn anode SEI structure for achieving stable ZIB. Specifically, β-CD with macrocyclic structure holds appropriate cavity size and charge distribution to encase OTf- anions at the Zn metal surface to form β-CD@OTf- dominated inner Helmholtz structure. Meanwhile, the electrochemically triggered β-CD@OTf- decomposition could in situ convert to the organic-inorganic hybrid SEI (ZnF2/ZnCO3/ZnS‒(C-O-C/*CF/*CF3)), which could efficiently hinder the Zn dendrite growth with maintain the proper SEI mechanical strength stability to guarantee the long-term stability. The thus-derived Zn | |Zn pouch cell (21 cm2 size) with β-CD-containing electrolyte exhibits a cumulative capacity of 6450 mAh-2 cm-2 at conditions of 10 mAh cm-2 high areal capacity. This work gives insights for reaching stable ZIB via electrolyte additive triggered SEI structure regulation.