Nonplanar π-Conjugated Sulfur Heterocyclic Quinone Polymer Cathode for Air-Rechargeable Zinc/Organic Battery with Simultaneously Boosted Output Voltage, Rate Capability, and Cycling Life

共轭体系 杂原子 材料科学 阴极 聚合 有机自由基电池 轨道能级差 光化学 咔唑 电子转移 聚合物 离域电子 电化学 化学 有机化学 电极 物理化学 分子 戒指(化学)
作者
Xin Shi,Ang Yi,Qiyu Liu,Yan Zhang,Shiwei Lin,Xihong Lu
出处
期刊:ACS Nano [American Chemical Society]
卷期号:17 (24): 25005-25013 被引量:4
标识
DOI:10.1021/acsnano.3c07346
摘要

π-conjugated organic compounds with a good charge transfer ability and rich redox functional groups are promising cathode candidates for air-rechargeable aqueous Zn-based batteries (AAZBs). However, the output voltage of even the state-of-the-art π-conjugated organic cathodes lies well below 0.8 V, resulting in insufficient energy density. Herein, we design a nonplanar π-conjugated sulfur heterocyclic quinone polymer (SHQP) as an advanced cathode material for AAZBs by polymerization 1,4-Benzoquinone (BQ) and S heteroatoms periodically. The extended π-conjugated plane and enhanced aromaticity endow SHQP with a more sensitive charge transfer ability and robust structure. Furthermore, the delocalized π electrons in the whole system are insufficient as the π orbit of the S heteroatom is not in the same plane with the π orbit of BQ due to its folded configuration, resulting in negligible variation of electron density around C═O after the polymerization. Thus, the output voltage of SHQP shows no significant decrease even though the thioether bond (-S-) functions as electron donor. Consequently, the Zn/SHQP AAZBs can deliver a record high midpoint discharging voltage (0.95 V), rate performance (119 mAh g-1 at 10 A g-1), and durability (98.7% capacity retention after 200 cycles) across a wide temperature range.
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