Xhesilda Fataj, Andreas J. Achazi, Christian Stolze, Simon Muench, René Burges, Ilya Anufriev, Manon Mignon, Doreen Mollenhauer, Ivo Nischang, Martin D. Hager and Ulrich S. Schubert*,
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引用次数: 0
Abstract
In search of anode materials for organic batteries, we propose benzoxazole-based redox-active polymers. We report theoretically calculated redox properties of the monomer and polymer based on small polymer chain models using density functional theory (DFT). Subsequently, a straightforward synthesis of poly(4-(benzoxazol-2-yl)-1-(4-vinyl benzyl)pyridinium chloride) (PBO) via radical polymerization is presented. To our knowledge, PBO is the first representative of this class of redox-active polymers applied in batteries, and it has a theoretical specific capacity of 76.8 mA h g–1 (first redox process). PBO was utilized as an anode and capacity-limiting electrode in an all-organic radical battery using aqueous- and organic-based electrolytes as well as 2,2,6,6-tetramethylpiperidinyl-N-oxy (TEMPO) derivatives as cathodes, providing a cell voltage of 1.3 and 1.4 V in aqueous- and organic-based electrolytes, respectively. The material revealed 99% capacity utilization at 1 C in the first cycle using an organic electrolyte (1 M LiClO4 in CH3CN) and more than 75% capacity utilization in an aqueous electrolyte (1 M LiClO4 in H2O). In both systems, after rate capability tests (from 0.2 to 50 C), the cells were cycled again at 1 C, where 50% of the initial capacity was retained after 100 cycles. Even though, due to the linearity and the molar mass of PBO, a capacity decay is observed during cycling tests, this study opens a promising class of molecules for the development of anode materials.
为了寻找有机电池的负极材料,我们提出了基于苯并恶唑的氧化还原活性聚合物。我们报告了基于密度泛函理论(DFT)小聚合物链模型的单体和聚合物氧化还原特性的理论计算结果。随后,我们介绍了通过自由基聚合直接合成聚(4-(苯并恶唑-2-基)-1-(4-乙烯基苄基)吡啶氯化物)(PBO)的方法。据我们所知,PBO 是这一类氧化还原活性聚合物中第一个应用于电池的代表,其理论比容量为 76.8 mA h g-1(第一氧化还原过程)。在使用水基和有机基电解质以及 2,2,6,6- 四甲基哌啶基-N-氧基(TEMPO)衍生物作为阴极的全有机自由基电池中,PBO 被用作阳极和容量限制电极,在水基和有机基电解质中的电池电压分别为 1.3 V 和 1.4 V。在使用有机电解质(1 M LiClO4 in CH3CN)的第一个循环中,该材料在 1 C 下的容量利用率为 99%,而在水基电解质(1 M LiClO4 in H2O)中的容量利用率超过 75%。在这两种系统中,经过速率能力测试(从 0.2 到 50 摄氏度)后,电池在 1 摄氏度下再次循环,100 次循环后仍能保持 50%的初始容量。尽管由于 PBO 的线性和摩尔质量,在循环测试过程中会出现容量衰减,但这项研究为开发阳极材料开辟了一类前景广阔的分子。
期刊介绍:
ACS Applied Energy Materials is an interdisciplinary journal publishing original research covering all aspects of materials, engineering, chemistry, physics and biology relevant to energy conversion and storage. The journal is devoted to reports of new and original experimental and theoretical research of an applied nature that integrate knowledge in the areas of materials, engineering, physics, bioscience, and chemistry into important energy applications.