Innovation in the development of electrochemical energy storage methods is essential if these technologies are to meet the variable needs of the electrical grid. Nonaqueous redox flow batteries represent an underdeveloped area of research in energy storage—one which has seen a recent spike in interest owing to the potential for modular, energy-dense electrochemical energy conversion. Here, we summarize our recent work, focused on the design of polyoxovanadate-alkoxide clusters [V₆O₇(OR)₁₂] as a new class of charge carrier for nonaqueous energy storage. The synthetic strategies we have employed, including homoleptic ligand substitution, selective ligand functionalization, and heterometal installation, demonstrate the flexibility of this hexametalate platform, and result in significant improvement of molecular properties with relevance to flow battery energy density. The identified homoleptic surface modifications (substituting R = CH₃ for R = C₂H₅) to the polyoxovanadate-alkoxide scaffold yield an increase in stable operating voltage window (from 0.6 V to 1.8 V), as well as an increase in the stoichiometric number of electrons that can be stored at each battery electrode (from 1 to 2). Targeted functionalization at the cluster surface with an ether-based ligand affords [V₆O₇(OC₂H₅)₉(OCH₂)₃CCH₂OC₂H₄OCH₃], which demonstrates a 12-fold increase in solubility over its homoleptic congener, from 0.05 to 0.60 M in acetonitrile. The substitution of a titanium center into the hexametalate core to generate [V₅TiO₆(OCH₃)₁₃]⁻ further increases the voltage window to 2.3 V, as new heterometal-based redox events are introduced to the profile. Through these studies, we have gained valuable insights into the molecular parameters that determine the energy storage capabilities of multimetallic charge carriers. Collectively, our results highlight new opportunities for polynuclear charge carriers, and emphasize the critical role that synthetic inorganic chemistry plays in the development of effective nonaqueous redox flow battery technologies.

如果这些技术要满足电网不断变化的需求，那么开发电化学储能方法的创新就必不可少。非水氧化还原液流电池代表了能量存储研究的欠发达领域，由于模块化，能量密集的电化学能量转换的潜力，近来人们对它的兴趣激增。在这里，我们总结了我们最近的工作，重点是聚氧钒酸盐-醇盐簇[V ₆ O ₇（OR）₁₂]作为用于非水能存储的新型电荷载体。我们采用的合成策略包括均相配体取代，选择性配体官能化和杂金属安装，证明了该六金属酸盐平台的灵活性，并显着改善了与液流电池能量密度相关的分子性能。鉴定的均质表面改性（用R = CH ₃代替R = C ₂ H ₅）到聚氧钒酸盐-醇盐支架上的稳定工作电压窗口增加（从0.6 V到1.8 V），以及可以存储在每个电池电极上的电子的化学计量数增加（从1到2）。使用基于醚的配体在簇表面进行靶向官能化可提供[V ₆ O ₇（OC ₂ H ₅）₉（OCH ₂）₃ CCH ₂ OC ₂ H ₄ OCH ₃]，这表明其溶解度比其均相同类物高，在乙腈中从0.05增至0.60M。将钛中心置换成六金属酸盐核以生成[V ₅ TiO ₆（OCH ₃）₁₃ ] ^-随着新的基于杂金属的氧化还原事件被引入到配置文件中，电压窗口进一步增加到2.3V。通过这些研究，我们获得了确定多金属电荷载体储能能力的分子参数的宝贵见解。总的来说，我们的结果突出了多核电荷载体的新机遇，并强调了合成无机化学在有效的非水氧化还原液流电池技术发展中所起的关键作用。