Intrinsic Hydrogen-Bond Donors-Lined Organophosphate Superionic Nanochannels Levering High-Rate-Endurable Aqueous Zn Batteries

摘要

Organic/inorganic hybrid artificial functional layer (AFL) designs of Zn anodehave witnessed good progress in stabilizing the Zn anode. However, such processesremain uncapable of simultaneously providing durable protection and fastZn~(2+) migration, especially in high-rate scenarios. Herein, intrinsic hydrogen-bonddonor (HBD)-lined organophosphate superionic nanochannels are initially engineeredto address this challenge. Due to unique ordered nanochannels with asmaller diameter than that of hydrated Zn~(2+) ions and polyanions, hydroxymethylZn phosphates (Zn(O_3PCH_2OH, ZnOPC) are first considered for AFL design. Thesmall size can provide an interception for polyanions. Density functional theorycalculation indicates that ZnOPC nanochannels possess a 35 lower Zn~(2+) migrationenergy barrier than conventional Zn phosphate, highly consistent with testedresults. Additionally, as HBDs, rich -CH_2OH groups located at nanochannelsimpose a targeted hydrogen-bonding interaction with water molecules. Consequently,at an ultrahigh current density up to 50 mA cm~(?2), the Zn@ZnOPC anodeshows a 36 lower overpotential than that of the bare Zn anode. As-assembledZn @ ZnOPC//NaV3O8 · 1.5H_2O full cells exhibit an ultralong lifespan of20 000 cycles at 20 A g~(?1), with a low capacity-decay of 0.016 per cycle. This workfeatures a targeted hydrogen bonding-enhanced desolvation effect occurring inorganophosphate superionic nanochannels, which would enlighten to explorereliable fast-charging aqueous batteries.