@article{ae30ddd88d0948278570c05620a09d29,
title = "Stable, Impermeable Hexacyanoferrate Anolyte for Nonaqueous Redox Flow Batteries",
abstract = "Redox-active molecules, or redoxmers, in nonaqueous redox flow batteries often suffer from membrane crossover and low electrochemical stability. Transforming inorganic polyionic redoxmers established for aqueous batteries into nonaqueous candidates is an attractive strategy to address these challenges. Here we demonstrate such tailoring for hexacyanoferrate (HCF) by pairing the anions with tetra-n-butylammonium cation (TBA+). TBA3HCF has good solubility in acetonitrile and >1 V lower redox potential vs the aqueous counterpart; thus, the familiar aqueous catholyte becomes a new nonaqueous anolyte. The lowering of redox potential correlates with replacement of water by acetonitrile in the solvation shell of HCF, which can be traced to H-bond formation between water and cyanide ligands. Symmetric flow cells indicate exceptional stability of HCF polyanions in nonaqueous electrolytes and Nafion membranes completely block HCF crossover in full cells. Ion pairing of metal complexes with organic counterions can be effective for developing promising redoxmers for nonaqueous flow batteries.",
author = "Yuyue Zhao and Bheemireddy, {Sambasiva R.} and Diqing Yue and Zhou Yu and Uddin, {Mohammad Afsar} and Haoyu Liu and Zhiguang Li and Xiaoting Fang and Xingyi Lyu and Garvit Agarwal and Zhangxing Shi and Robertson, {Lily A.} and Lei Cheng and Tao Li and Assary, {Rajeev S.} and Venkat Srinivasan and Babinec, {Susan J.} and Zhengcheng Zhang and Moore, {Jeffrey S.} and Shkrob, {Ilya A.} and Xiaoliang Wei and Lu Zhang",
note = "This work was financially supported by the National Science Foundation (Award No. CHE-2055222) and the Joint Center for Energy Storage Research (JCESR), an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Science, and Basic Energy Sciences. This research was also supported by Laboratory Directed Research and Development (LDRD) funding from Argonne National Laboratory, provided by the Director, Office of Science, of the U.S. Department of Energy under Contract No. DE-AC02-06CH11357. We acknowledge a generous grant of computer time from the Argonne National Laboratory Computing Resource Center (Bebop). We also acknowledge the computational resources from Center for Nanoscale Materials, an Office of Science user facility, which was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. The submitted manuscript has been created by UChicago Argonne, LLC, Operator of Argonne National Laboratory (\u201CArgonne\u201D). Argonne, a U.S. Department of Energy Office of Science laboratory, is operated under Contract No. DE-AC02-06CH11357.",
year = "2024",
month = sep,
day = "13",
doi = "10.1021/acsenergylett.4c01351",
language = "English (US)",
volume = "9",
pages = "4273--4279",
journal = "ACS Energy Letters",
issn = "2380-8195",
publisher = "American Chemical Society",
number = "9",
}