Improved solubility of titanium-doped polyoxovanadate charge carriers for symmetric non-aqueous redox flow batteries
Improved solubility of titanium-doped polyoxovanadate charge carriers for symmetric non-aqueous redox flow batteries
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提高对称非水氧化还原液流电池中钛掺杂多氧钒酸盐电荷载体的溶解度
DOI：
10.1039/d3dt03642a
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发表时间：
2023
影响因子：
4
通讯作者：
Matson, Ellen M.
中科院分区：
文献类型：
--
作者：
Dagar, Mamta;Dissanyake, D. M.;Kesler, Daniel N.;Corr, Molly;McPherson, Joshua D.;Brennessel, William W.;McKone, James R.;Matson, Ellen M.
非水氧化还原液流电池由于能够实现比在水中容易获得的更大的电池电压，因此构成了电网规模能量存储的有前途的解决方案。然而，它们的广泛应用受到电活性物质在有机溶剂中的低溶解度的限制。在这项工作中，我们证明了钛取代的多氧钒酸盐-醇盐簇的有机官能化增加了这些组装体在乙腈中的溶解度，超过其均配同系物的溶解度>10倍。循环伏安法，计时电流法，和充放电循环实验的报告，评估这些集群的电化学性能相关的能力，作为多电子电荷载体的能量存储。配位体变化的动力学影响进行评估，证明在混合金属电荷载体的扩散性和异质性的电子转移速率的配位体结构的作用。我们的研究结果提供了新的见解，这些组件的物理化学性质的结构修饰的影响。
Non-aqueous redox flow batteries constitute a promising solution for grid-scale energy storage due to the ability to achieve larger cell voltages than can be readily accessed in water. However, their widespread application is limited by low solubility of the electroactive species in organic solvents. In this work, we demonstrate that organic functionalization of titanium-substituted polyoxovanadate-alkoxide clusters increases the solubility of these assemblies over that of their homoleptic congeners by a factor of >10 in acetonitrile. Cyclic voltammetry, chronoamperometry, and charge–discharge cycling experiments are reported, assessing the electrochemical properties of these clusters relevant to their ability to serve as multielectron charge carriers for energy storage. The kinetic implications of ligand variation are assessed, demonstrating the role of ligand structure on the diffusivity and heterogeneous rates of electron transfer in mixed-metal charge carriers. Our results offer new insights into the impact of structural modifications on the physicochemical properties of these assemblies.