Intrinsic Hydrogen‐Bond Donors‐Lined Organophosphate Superionic Nanochannels Levering High‐Rate‐Endurable Aqueous Zn Batteries. Issue 46 (13th October 2022)

• Record Type: Journal Article
• Authors: He, Jiangfeng; Tang, Yongchao; Liu, Guigui; Li, Hongqing; Ye, Minghui; Zhang, Yufei; Yang, Qi; Liu, Xiaoqing; Li, Chengchao
• Is Part Of: Advanced energy materials. Volume 12:Issue 46(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-10-13
• Subjects: aqueous Zn batteries -- artificial functional layers -- hydrogen‐bond donors -- hydroxymethyl Zn phosphate -- superionic nanochannels; Energy harvesting -- Materials -- Periodicals; Energy conversion -- Materials -- Periodicals; Energy storage -- Materials -- Periodicals; Photovoltaics -- Periodicals; Fuel cells -- Periodicals; Thermoelectric materials -- Periodicals; 621.31
• DOI: 10.1002/aenm.202202661
• Languages: English
• ISSNs: 1614-6832

Abstract

Abstract: Organic/inorganic hybrid artificial functional layer (AFL) designs of Zn anode have witnessed good progress in stabilizing the Zn anode. However, such processes remain uncapable of simultaneously providing durable protection and fast Zn 2+ migration, especially in high‐rate scenarios. Herein, intrinsic hydrogen‐bond donor (HBD)‐lined organophosphate superionic nanochannels are initially engineered to address this challenge. Due to unique ordered nanochannels with a smaller diameter than that of hydrated Zn 2+ ions and polyanions, hydroxymethyl Zn phosphates (Zn(O3 PCH2 OH, ZnOPC) are first considered for AFL design. The small size can provide an interception for polyanions. Density functional theory calculation indicates that ZnOPC nanochannels possess a 35% lower Zn 2+ migration energy barrier than conventional Zn phosphate, highly consistent with tested results. Additionally, as HBDs, rich ‐CH2 OH groups located at nanochannels impose a targeted hydrogen‐bonding interaction with water molecules. Consequently, at an ultrahigh current density up to 50 mA cm −2, the Zn@ZnOPC anode shows a 36% lower overpotential than that of the bare Zn anode. As‐assembled Zn @ ZnOPC//NaV3 O8 · 1.5H2 O full cells exhibit an ultralong lifespan of 20 000 cycles at 20 A g −1, with a low capacity‐decay of 0.016% per cycle. This work features a targeted hydrogen bonding‐enhanced desolvation effect occurring in organophosphate superionic nanochannels, which would enlighten to explore reliable fast‐charging aqueous batteries. Abstract : Using hydroxymethyl Zn phosphates (ZnOPC) with unique ordered nanochannels, intrinsic hydrogen‐bond donor‐lined organophosphate superionic nanochannels are initially engineered to stabilize the Zn anode. Due to the low Zn 2+ migration energy barrier and targeted hydrogen bonding‐facilitated desolvation effect in ZnOPC nanochannels, the Zn@ZnOPC anode shows a remarkably enhanced high‐rate‐endurability and lifespan. This work would inspire to explore reliable fast‐charging aqueous batteries.