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Vol. 15 (2023)

Molecular Engineering Design for High-Performance Aqueous Zinc-Organic Battery

https://doi.org/10.1007/s40820-022-01009-x
Tianjiang Sun
Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), College of Chemistry, Haihe Laboratory of Sustainable Chemical Transformations, Renewable Energy Conversion and Storage Center, Nankai University, Tianjin 300071, People’s Republic of China
Weijia Zhang
Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), College of Chemistry, Haihe Laboratory of Sustainable Chemical Transformations, Renewable Energy Conversion and Storage Center, Nankai University, Tianjin 300071, People’s Republic of China
Qingshun Nian
CAS Key Laboratory of Materials for Energy Conversion, Department of Materials Science and Engineering, Hefei National Laboratory for Physical Science at the Microscale, University of Science and Technology of China Hefei, Hefei 230026, Anhui, People’s Republic of China
Zhanliang Tao
Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), College of Chemistry, Haihe Laboratory of Sustainable Chemical Transformations, Renewable Energy Conversion and Storage Center, Nankai University, Tianjin 300071, People’s Republic of China

Corresponding Author: Zhanliang Tao

taozhl@nankai.edu.cn

Nano-Micro Letters, Vol. 15 (2023), Article Number: 36

Abstract

Novel small sulfur heterocyclic quinones (6a,16a-dihydrobenzo[b]naphtho[2′,3′:5,6][1,4]dithiino[2,3-i]thianthrene-5,7,9,14,16,18-hexaone (4S6Q) and benzo[b]naphtho[2′,3′:5,6][1,4]dithiino[2,3-i]thianthrene-5,9,14,18-tetraone (4S4Q)) are developed by molecule structural design method and as cathode for aqueous zinc-organic batteries. The conjugated thioether (–S–) bonds as connected units not only improve the conductivity of compounds but also inhibit their dissolution by both extended π-conjugated plane and constructed flexible molecular skeleton. Hence, the Zn//4S6Q and Zn//4S4Q batteries exhibit satisfactory electrochemical performance based on 3.5 mol L−1 (M) Zn(ClO4)2 electrolyte. For instance, the Zn//4S6Q battery obtains 240 and 208.6 mAh g−1 of discharge capacity at 150 mA g−1 and 30 A g−1, respectively. The excellent rate capability is ascribed to the fast reaction kinetics. This system displays a superlong life of 20,000 cycles with no capacity fading at 3 A g−1. Additionally, the H+-storage mechanism of the 4S6Q compound is demonstrated by ex situ analyses and density functional theory calculations. Impressively, the battery can normally work at − 60 °C benefiting from the anti-freezing electrolyte and maintain a high discharge capacity of 201.7 mAh g−1, which is 86.2% of discharge capacity at 25 °C. The cutting-edge electrochemical performances of these novel compounds make them alternative electrode materials for Zn-organic batteries.


Highlights:


1 The conjugated thioether (–S–) bonds as connected units not only improve the conductivity of compounds but also inhibit their dissolution by both extended π-conjugated plane and constructed flexible molecular skeleton.
2 The Zn//4S6Q battery based on 3.5 M Zn(ClO4)2 electrolyte shows excellent rate capacity (208.6 mAh g−1 at 30 A g−1), superlong cycling life (> 20,000 cycles with no capacity fading), and impressive low-temperature performance (201.7 mAh g−1 at − 60 °C).
3 The H+-storage mechanism of 4S6Q compound is demonstrated by comprehensive characterizations.

Keywords

Aqueous Zn-organic battery Small sulfur heterocyclic quinones Conjugated thioether skeleton Superlong cycling life H -involved mechanism − 60 °C
Sun, Tianjiang, Weijia Zhang, Qingshun Nian, and Zhanliang Tao. 2023. “Molecular Engineering Design for High-Performance Aqueous Zinc-Organic Battery”. Nano-Micro Letters 15 (January):36. https://doi.org/10.1007/s40820-022-01009-x.
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