Benzotrithiophene-sulfonate covalent-organic frameworks: Supramolecular proton pumps for high-rate aqueous zinc-ion energy storage systems

Abstract

Proton chemistry is becoming a focal point in the development of zinc-ion energy storage devices due to its swift H⁺ insertion/extraction kinetics. This characteristic feature confers to electrodes a remarkable power density, rate capability, and prolonged cycling durability. However, the storage mechanism of H⁺ in electrodes based on covalent-organic frameworks (COFs) has not been thoroughly investigated. In this work, we introduce an unprecedented concept involving a supramolecular approach based on the design of a benzotrithiophene-sulfonate COF (COF-BTT-SO₃H) with remarkable storage capacity for simultaneous insertion and extraction of H⁺ and Zn²⁺. The ad hoc positioning of the -SO₃H groups within the COF-BTT-SO₃H structure facilitates the formation of a robust H-bonded network. Through density functional theory calculations and employing in situ and ex situ analyses, we demonstrate that this network functions as a spontaneous proton ion pump leading to enhanced ion-diffusion kinetics and exceptional rate performance in zinc-ion energy storage devices. COF-BTT-SO₃H reveals a high capacity of 294.7 mA h/g (0.1 A/g), a remarkable maximum energy density of 182.5 W h/kg, and power density of 14.8 kW/kg, which are superior to most of the reported COF-based electrodes or other organic and inorganic electrode materials in Zn²⁺ energy storage devices.

Keywords

charge storage mechanism / covalent-organic frameworks / functional porous materials / proton pump / zinc-ion energy storage devices

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