Ultra-long cycle life organic-sodium batteries enabled by thiophene-based porphyrin in-situ electropolymerization

Ultra-long cycle life organic-sodium batteries enabled by thiophene-based porphyrin in-situ electropolymerization
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噻吩基卟啉原位电聚合实现超长循环寿命有机钠电池

DOI:
10.1016/j.cej.2022.139951
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发表时间:
2022-10
影响因子:
15.1
通讯作者:
Ping Gao
Ping Gao
中科院分区:
工程技术1区
文献类型:
--
作者:
Youlian Zeng;Jiarong Zhou;Jiahao Zhang;Fangfang He;Yachao Su;Pu Wang;Songting Tan;Ping Gao

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有机钠电池因其丰富的钠资源和有机材料的分子可调性而受到广泛关注。然而,有机材料在电解质中的溶解性和低的电子电导率限制了其发展。在此,提出了[5,15-二(噻吩-2-基)卟啉] M(II)(MTP,M = Cu,Ni)的卟啉络合物作为用于有机钠电池的高度稳定的阴极材料。得益于金属卟啉络合物的多次电子转移和卟啉络合物的噻吩基团在初始循环中的原位聚合,CuTP阴极在100 mA g− 1下提供203 mAh/g的可逆容量,并且由于原位聚合过程诱导的增强的共轭结构,在5 A/g的高电流密度下提供高达11,000次循环的长期循环稳定性。金属卟啉基阴极的比能量密度为508 Wh kg− 1,功率密度为18 KW kg− 1。通过实验和模拟研究,对MTP阴极的电荷储存位点和原位聚合机理进行了系统的评价。该研究为解决有机阴极的溶解问题和提高有机钠电池的循环稳定性提供了新的策略。
Organic-sodium batteries have attracted extensive attention due to the abundance of sodium resource and the molecular tunability of organic materials. However, the dissolution of organic materials in electrolytes and low electronic conductivity limit its development. Here, a porphyrin complex of [5,15-di(thiophen-2-yl) porphinato] M(II) (MTP, M = Cu, Ni) is proposed as highly stable cathode material for organic-sodium batteries. Benefiting from the multiple electron transfer of metal porphyrin complex and in-situ polymerization of thiophene groups of porphyrin complex in initial cycles, the CuTP cathode delivers a reversible capacity of 203 mAh/g at 100 mA g−1and long-term cycling stability up to 11,000 cycles at a high current density of 5 A/g owing to the enhanced conjugated structure induced by in situ polymerization process. A specific energy density of 508 Wh kg−1and a power density of 18 KW kg−1are achieved for metal porphyrin-based cathode. The charge storage sites and in-situ polymerization mechanism of MTP cathode are systematically evaluated by both experimental and simulated studies. This study would provide a new strategy to address the dissolution issue of organic cathode and improve cycling stability of the organic-sodium batteries.
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