A High-Rate Two-Dimensional Polyarylimide Covalent Organic Framework Anode for Aqueous Zn-Ion Energy Storage Devices

Minghao Yu; Naisa Chandrasekhar; Ramya Kormath Madam Raghupathy; Khoa Hoang Ly; Haozhe Zhang; Evgenia Dmitrieva; Chaolun Liang; Xihong Lu; Thomas D Kühne; Hossein Mirhosseini; Inez M Weidinger; Xinliang Feng

doi:10.1021/jacs.0c07992

A High-Rate Two-Dimensional Polyarylimide Covalent Organic Framework Anode for Aqueous Zn-Ion Energy Storage Devices

J Am Chem Soc. 2020 Nov 18;142(46):19570-19578. doi: 10.1021/jacs.0c07992. Epub 2020 Nov 9.

Affiliations

¹ Center for Advancing Electronics Dresden (cfaed) & Faculty of Chemistry and Food Chemistry, Technische Universität Dresden, 01062 Dresden, Germany.
² Dynamics of Condensed Matter and Center for Sustainable Systems Design, Chair of Theoretical Chemistry, University of Paderborn, Warburger Strasse 100, 33098 Paderborn, Germany.
³ MOE of the Key Laboratory of Bioinorganic and Synthetic Chemistry, The Key Lab of Low-carbon Chem & Energy Conservation of Guangdong Province, KLGHEI of Environment and Energy Chemistry, School of Chemistry, Sun Yat-sen University, Guangzhou 510275, China.
⁴ Center of Spectroelectrochemistry, Leibniz Institute for Solid State and Materials Research (IFW) Dresden, Helmholtzstrasse 20, 01069 Dresden, Germany.
⁵ Instrumental Analysis and Research Centre, Sun Yat-sen University, Guangzhou 510275, China.

PMID: 33164490
DOI: 10.1021/jacs.0c07992

Abstract

Rechargeable aqueous Zn-ion energy storage devices are promising candidates for next-generation energy storage technologies. However, the lack of highly reversible Zn²⁺-storage anode materials with low potential windows remains a primary concern. Here, we report a two-dimensional polyarylimide covalent organic framework (PI-COF) anode with high-kinetics Zn²⁺-storage capability. The well-organized pore channels of PI-COF allow the high accessibility of the build-in redox-active carbonyl groups and efficient ion diffusion with a low energy barrier. The constructed PI-COF anode exhibits a specific capacity (332 C g^-1 or 92 mAh g^-1 at 0.7 A g^-1), a high rate capability (79.8% at 7 A g^-1), and a long cycle life (85% over 4000 cycles). In situ Raman investigation and first-principle calculations clarify the two-step Zn²⁺-storage mechanism, in which imide carbonyl groups reversibly form negatively charged enolates. Dendrite-free full Zn-ion devices are fabricated by coupling PI-COF anodes with MnO₂ cathodes, delivering excellent energy densities (23.9 ∼ 66.5 Wh kg^-1) and supercapacitor-level power densities (133 ∼ 4782 W kg^-1). This study demonstrates the feasibility of covalent organic framework as Zn²⁺-storage anodes and shows a promising prospect for constructing reliable aqueous energy storage devices.