Stabilization of Naphthalene Diimide Anions by Ion Pair Formation in Nonaqueous Organic Redox Flow Batteries

被引:6
作者
Ahn, Seongmo [1 ]
Son, Mina [1 ,2 ]
Singh, Vikram [1 ]
Yun, Ariyeong [1 ]
Baik, Mu-Hyun [1 ,2 ]
Byon, Hye Ryung [1 ]
机构
[1] Korea Adv Inst Sci & Technol KAIST, Dept Chem, Daejeon 34141, South Korea
[2] Inst Basic Sci IBS, Ctr Catalyt Hydrocarbon Functionalizat, Daejeon 34141, South Korea
基金
新加坡国家研究基金会;
关键词
MOLECULAR-ORBITAL METHODS; BASIS-SET; RATIONAL DESIGN; DENSITY; STORAGE; ANOLYTE; ENERGY; LI+;
D O I
10.1021/jacs.3c11176
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
In redox flow batteries, a compelling strategy for enhancing the charge capacity of redox-active organic molecules involves storing multiple electrons within a single molecule. However, this approach poses unique challenges such as chemical instability by forming radicals, elevated energy requirements, and unsustainable charge concentration. Ion pairing is a possible solution to achieve charge neutrality and engineer redox potential shifts but has received limited attention. In this study, we demonstrate that Li+ can stabilize naphthalene diimide (NDI) anions dissolved in acetonitrile and significantly shift the second cathodic potential close to the first. Our findings, supported by density functional theory calculations and Fourier transform infrared spectroscopy, indicate that dimeric NDI species form stable ion pairs with Li+. Conversely, K+ ions exhibit weak interactions, and cyclic voltammograms confirm significant potential shifts when stronger Lewis acids and solvents with lower donor numbers are employed. Galvanostatic examinations reveal a single voltage plateau with Li+, which indicates a rapid redox process involving doubly charged NDI2- with Li+. These aggregated ion pairs offer the additional benefits of hindering crossover events, contributing to excellent cyclability, and suppressing undesirable side reactions even after 1000 redox cycles.
引用
收藏
页码:4521 / 4531
页数:11
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