Sariyer Selin, Ghosh Arpita, Dambasan Sevde Nazli, Halim El Mahdi, El Rhazi Mama, Perrot Hubert, Sel Ozlem, Demir-Cakan Rezan
Department of Chemical Engineering, Gebze Technical University, 41400 Gebze, Kocaeli, Turkey.
Laboratoire Interfaces et Systèmes Electrochimiques, LISE, Sorbonne Université, CNRS, 75005 Paris, France.
ACS Appl Mater Interfaces. 2022 Feb 16;14(6):8508-8520. doi: 10.1021/acsami.1c19607. Epub 2022 Feb 4.
Rechargeable batteries employing aqueous electrolytes are more reliable and cost-effective as well as possess high ionic conductivity compared to the flammable organic electrolyte solutions. Among these types of batteries, aqueous batteries with multivalent ions attract more attention in terms of providing high energy density. Herein, electrochemical behavior of an organic electrode based on a highly aromatic polymer containing 2,3-diaminophenazine repeating unit, namely poly(-phenylenediamine) (PoPD), is tested in two different multivalent ions (Zn and Al) containing aqueous electrolytes, that is, in zinc sulfate and aluminum chloride solutions. PoPD is synthesized via electropolymerization, and its ion transport and storage mechanism are comprehensively investigated by structural and electrochemical analyses. The electrochemical quartz crystal microbalance, time-dependent Fourier transform infrared, and electrochemical impedance spectroscopy analyses as well as X-ray diffraction observations established that along with the Zn or Al ions, reversible proton insertion/extraction also takes place. Contrary to the most of the organic electrodes that requires the use of conductive carbon additives, the electrodeposited PoPD electrode is intrinsically electrically conductive enough, resulting in a binder and additive free electrode assembly. In addition, its discharge products do not dissolve in aqueous medium. As a whole, the resulting PoPD electrode delivers excellent rate performances with prolonged cycle life in which discharge capacities of ∼110 mAh g in 0.25 M AlCl and ∼93 mAh g in 1 M ZnSO aqueous electrolyte after 1000 cycles at a current density of 5C have been achieved.
与易燃的有机电解质溶液相比，采用水性电解质的可充电电池更可靠、更具成本效益，并且具有高离子电导率。在这类电池中，含多价离子的水性电池在提供高能量密度方面更受关注。在此，基于含有2,3-二氨基吩嗪重复单元的高度芳香族聚合物（即聚对苯二胺，PoPD）的有机电极，在两种不同的含多价离子（锌和铝）的水性电解质中进行了测试，即在硫酸锌和氯化铝溶液中。PoPD通过电聚合合成，并通过结构和电化学分析对其离子传输和存储机制进行了全面研究。电化学石英晶体微天平、时间分辨傅里叶变换红外光谱和电化学阻抗谱分析以及X射线衍射观察结果表明，除了锌或铝离子外，还发生了可逆的质子插入/脱出。与大多数需要使用导电碳添加剂的有机电极不同，电沉积的PoPD电极本身具有足够的导电性，从而形成了无粘结剂和添加剂的电极组件。此外，其放电产物不溶于水性介质。总体而言，所得的PoPD电极在长循环寿命下具有出色的倍率性能，在5C电流密度下经过1000次循环后，在0.25M AlCl3和1M ZnSO4水性电解质中的放电容量分别达到约110 mAh g和约93 mAh g。
