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Vol. 14 (2022)

Supramolecular Polymer Intertwined Free-Standing Bifunctional Membrane Catalysts for All-Temperature Flexible Zn–Air Batteries

https://doi.org/10.1007/s40820-022-00927-0
Nayantara K. Wagh
Department of Materials Science and Chemical Engineering, Hanyang University, Ansan, Republic of Korea
Sambhaji S. Shinde
Department of Materials Science and Chemical Engineering, Hanyang University, Ansan, Republic of Korea
Chi Ho Lee
Department of Applied Chemistry, Center for Bionano Intelligence Education and Research, Hanyang University, Ansan, Republic of Korea
Sung‑Hae Kim
Department of Materials Science and Chemical Engineering, Hanyang University, Ansan, Republic of Korea
Dong‑Hyung Kim
Department of Materials Science and Chemical Engineering, Hanyang University, Ansan, Republic of Korea
Han‑Don Um
Department of Chemical Engineering, Kangwon National University, Chuncheon, Gangwon 24341, Republic of Korea
Sang Uck Lee
Department of Applied Chemistry, Center for Bionano Intelligence Education and Research, Hanyang University, Ansan, Republic of Korea
Jung‑Ho Lee
Department of Materials Science and Chemical Engineering, Hanyang University, Ansan, Republic of Korea

Corresponding Author: Jung‑Ho Lee

jungho@hanyang.ac.kr

Nano-Micro Letters, Vol. 14 (2022), Article Number: 190

Abstract

Rational construction of flexible free-standing electrocatalysts featuring long-lasting durability, high efficiency, and wide temperature tolerance under harsh practical operations are fundamentally significant for commercial zinc–air batteries. Here, 3D flexible free-standing bifunctional membrane electrocatalysts composed of covalently cross-linked supramolecular polymer networks with nitrogen-deficient carbon nitride nanotubes are fabricated (referred to as PEMAC@NDCN) by a facile self-templated approach. PEMAC@NDCN demonstrates the lowest reversible oxygen bifunctional activity of 0.61 V with exceptional long-lasting durability, which outperforms those of commercial Pt/C and RuO2. Theoretical calculations and control experiments reveal the boosted electron transfer, electrolyte mass/ion transports, and abundant active surface site preferences. Moreover, the constructed alkaline Zn–air battery with PEMAC@NDCN air–cathode reveals superb power density, capacity, and discharge–charge cycling stability (over 2160 cycles) compared to the reference Pt/C + RuO2. Solid-state Zn–air batteries enable a high power density of 211 mW cm−2, energy density of 1056 Wh kg−1, stable charge–discharge cycling of 2580 cycles for 50 mA cm−2, and wide temperature tolerance from − 40 to 70 °C with retention of 86% capacity compared to room-temperature counterparts, illustrating prospects over harsh operations.


Highlights:


1 Rational design of 3D flexible free-standing membrane catalysts with protonation between supramolecular polymers and nitrogen-deficient carbon nitride nanotubes frameworks via facile bottom-up self-conversion approach.
2 PEMAC@NDCN demonstrates the lowest reversible oxygen bifunctional activity of 0.61 V with exceptional long-lasting durability, surpassing the commercial and reported champion oxygen catalysts.
3 Engineering catalytically active cathode materials enabled all-temperature flexible Zn–air batteries with high electrochemical and mechanical performances (temperature of − 40 to 70 °C) under harsh operations.

Keywords

Flexible free-standing membrane electrocatalysts Supramolecular polymer Alkaline and flexible solid-state Zn–air batteries All-temperature operations High capacity and energy density
Wagh, Nayantara K., Sambhaji S. Shinde, Chi Ho Lee, Sung‑Hae Kim, Dong‑Hyung Kim, Han‑Don Um, Sang Uck Lee, and Jung‑Ho Lee. 2022. “Supramolecular Polymer Intertwined Free-Standing Bifunctional Membrane Catalysts for All-Temperature Flexible Zn–Air Batteries”. Nano-Micro Letters 14 (September):190. https://doi.org/10.1007/s40820-022-00927-0.
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