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一种基于吩嗪的共轭微孔聚合物,用作铝-有机电池的高性能阴极。

A phenazine-based conjugated microporous polymer as a high performing cathode for aluminium-organic batteries.

作者信息

Grieco Rebecca, Luzanin Olivera, Alvan Diego, Liras Marta, Dominko Robert, Patil Nagaraj, Bitenc Jan, Marcilla Rebeca

机构信息

Electrochemical Processes Unit, IMDEA Energy Institute, Avda. Ramón de La Sagra 3, 28935 Móstoles, Spain.

National Institute of Chemistry, Hajdrihova 19, 1000, Ljubljana, Slovenia.

出版信息

Faraday Discuss. 2024 Mar 11;250(0):110-128. doi: 10.1039/d3fd00132f.

Abstract

One of the possible solutions to circumvent the sluggish kinetics, low capacity, and poor integrity of inorganic cathodes commonly used in rechargeable aluminium batteries (RABs) is the use of redox-active polymers as cathodes. They are not only sustainable materials characterised by their structure tunability, but also exhibit a unique ion coordination redox mechanism that makes them versatile ion hosts suitable for voluminous aluminium cation complexes, as demonstrated by the poly(quinoyl) family. Recently, phenazine-based compounds have been found to have high capacity, reversibility and fast redox kinetics in aqueous electrolytes because of the presence of a CN double bond. Here, we present one of the first examples of a phenazine-based hybrid microporous polymer, referred to as IEP-27-SR, utilized as an organic cathode in an aluminium battery with an AlCl/EMIMCl ionic liquid electrolyte. The preliminary redox and charge storage mechanism of IEP-27-SR was confirmed by ATR-IR and EDS analyses. The introduction of phenazine active units in a robust microporous framework resulted in a remarkable rate capability (specific capacity of 116 mA h g at 0.5C with 77% capacity retention at 10C) and notable cycling stability, maintaining 75% of its initial capacity after 3440 charge-discharge cycles at 1C (127 days of continuous cycling). This superior performance compared to reported Al//n-type organic cathode RABs is attributed to the stable 3D porous microstructure and the presence of micro/mesoporosity in IEP-27-SR, which facilitates electrolyte permeability and improves kinetics.

摘要

可充电铝电池(RABs)中常用的无机阴极存在动力学迟缓、容量低和完整性差等问题,解决这些问题的一种可能方案是使用氧化还原活性聚合物作为阴极。它们不仅是以结构可调性为特征的可持续材料,而且还展现出独特的离子配位氧化还原机制,使其成为适用于大量铝阳离子络合物的通用离子主体,聚(喹啉)家族已证明了这一点。最近,由于存在CN双键,基于吩嗪的化合物在水性电解质中具有高容量、可逆性和快速氧化还原动力学。在此,我们展示了首个基于吩嗪的杂化微孔聚合物的例子,称为IEP - 27 - SR,它被用作具有AlCl/EMIMCl离子液体电解质的铝电池中的有机阴极。通过ATR - IR和EDS分析证实了IEP - 27 - SR的初步氧化还原和电荷存储机制。在坚固的微孔骨架中引入吩嗪活性单元,产生了显著的倍率性能(在0.5C时比容量为116 mA h g,在10C时容量保持率为77%)和显著的循环稳定性,在1C下经过3440次充放电循环(连续循环127天)后保持其初始容量的75%。与报道的Al//n型有机阴极RABs相比,这种优异性能归因于IEP - 27 - SR中稳定 的3D多孔微观结构以及微/介孔的存在,这有利于电解质渗透并改善动力学。

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