Progress in the Design of Polyoxovanadate-Alkoxides as Charge Carriers for Nonaqueous Redox Flow Batteries

IF 3.8 3区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Comments on Inorganic Chemistry Pub Date : 2019-03-04 DOI:10.1080/02603594.2019.1587612

L. E. VanGelder, Timothy R. Cook, E. Matson

{"title":"Progress in the Design of Polyoxovanadate-Alkoxides as Charge Carriers for Nonaqueous Redox Flow Batteries","authors":"L. E. VanGelder, Timothy R. Cook, E. Matson","doi":"10.1080/02603594.2019.1587612","DOIUrl":null,"url":null,"abstract":"ABSTRACT 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. TOC GRAPHICAL ABSTRACT","PeriodicalId":10481,"journal":{"name":"Comments on Inorganic Chemistry","volume":"39 1","pages":"51 - 89"},"PeriodicalIF":3.8000,"publicationDate":"2019-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"13","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Comments on Inorganic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1080/02603594.2019.1587612","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}

引用次数: 13

Abstract

ABSTRACT 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. TOC GRAPHICAL ABSTRACT

查看原文本刊更多论文

多钒氧烷氧化物非水氧化还原液流电池载流子设计进展

如果这些技术要满足电网的可变需求，在电化学储能方法的发展创新是必不可少的。非水氧化还原液流电池代表了能量存储研究的一个不发达领域，由于模块化，能量密集的电化学能量转换的潜力，最近引起了人们的兴趣。在这里，我们总结了我们最近的工作，重点是设计多氧钒酸盐-醇氧化合物簇[V6O7(OR)12]作为一类新的非水储能电荷载体。我们采用的合成策略，包括同色配体取代、选择性配体功能化和异金属安装，证明了这种六偏酸酯平台的灵活性，并导致与液流电池能量密度相关的分子性质的显著改善。所鉴定的聚钒酸盐-醇氧基支架的同相表面修饰(用R = CH3取代R = C2H5)增加了稳定的工作电压窗口(从0.6 V增加到1.8 V)，并增加了每个电池电极上可存储的电子的化学数量(从1到2)。用醚基配体在簇表面进行靶向功能化可以提供[V6O7(OC2H5)9(OCH2)3CCH2OC2H4OCH3]。其在乙腈中的溶解度从0.05 M增加到0.60 M，比同眠同系物增加了12倍。随着新的异质金属氧化还原事件被引入到谱线中，钛中心取代到六偏酸盐核心中生成[V5TiO6(OCH3)13]−进一步将电压窗口增加到2.3 V。通过这些研究，我们对决定多金属载流子储能能力的分子参数获得了有价值的见解。总之，我们的研究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开发有效的非水氧化还原液流电池技术中的关键作用。Toc图形摘要

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文求助全文

来源期刊

Comments on Inorganic Chemistry 化学-无机化学与核化学

CiteScore

9.00

自引率

1.90%

发文量

审稿时长

>12 weeks

期刊介绍： Comments on Inorganic Chemistry is intended as a vehicle for authoritatively written critical discussions of inorganic chemistry research. We publish focused articles of any length that critique or comment upon new concepts, or which introduce new interpretations or developments of long-standing concepts. “Comments” may contain critical discussions of previously published work, or original research that critiques existing concepts or introduces novel concepts. Through the medium of “comments,” the Editors encourage authors in any area of inorganic chemistry - synthesis, structure, spectroscopy, kinetics and mechanisms, theory - to write about their interests in a manner that is both personal and pedagogical. Comments is an excellent platform for younger inorganic chemists whose research is not yet widely known to describe their work, and add to the spectrum of Comments’ author profiles, which includes many well-established inorganic chemists.