Stable, Impermeable Hexacyanoferrate Anolyte for Nonaqueous Redox Flow Batteries

Yuyue Zhao; Sambasiva R. Bheemireddy; Diqing Yue; Zhou Yu; Mohammad Afsar Uddin; Haoyu Liu; Zhiguang Li; Xiaoting Fang; Xingyi Lyu; Garvit Agarwal; Zhangxing Shi; Lily A. Robertson; Lei Cheng; Tao Li; Rajeev S. Assary; Venkat Srinivasan; Susan J. Babinec; Zhengcheng Zhang; Jeffrey S. Moore; Ilya A. Shkrob; Xiaoliang Wei; Lu Zhang

doi:10.1021/acsenergylett.4c01351

Stable, Impermeable Hexacyanoferrate Anolyte for Nonaqueous Redox Flow Batteries

Yuyue Zhao
, Sambasiva R. Bheemireddy
, Diqing Yue
, Zhou Yu
, Mohammad Afsar Uddin
, Haoyu Liu
, Zhiguang Li
, Xiaoting Fang
, Xingyi Lyu
, Garvit Agarwal
, Zhangxing Shi
, Lily A. Robertson
, Lei Cheng
, Tao Li
, Rajeev S. Assary
, Venkat Srinivasan
, Susan J. Babinec
, Zhengcheng Zhang
, Jeffrey S. Moore
, Ilya A. Shkrob

Xiaoliang Wei, Lu Zhang

Research output: Contribution to journal › Article › peer-review

4 Scopus citations

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.

Original language	English
Pages (from-to)	4273-4279
Number of pages	7
Journal	ACS Energy Letters
Volume	9
Issue number	9
DOIs	https://doi.org/10.1021/acsenergylett.4c01351
State	Published - Sep 13 2024
Externally published	Yes

Funding

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 (“Argonne”). Argonne, a U.S. Department of Energy Office of Science laboratory, is operated under Contract No. DE-AC02-06CH11357.

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10.1021/acsenergylett.4c01351

Cite this

Zhao, Y., Bheemireddy, S. R., Yue, D., Yu, Z., Uddin, M. A., Liu, H., Li, Z., Fang, X., Lyu, X., Agarwal, G., Shi, Z., Robertson, L. A., Cheng, L., Li, T., Assary, R. S., Srinivasan, V., Babinec, S. J., Zhang, Z., Moore, J. S., ... Zhang, L. (2024). Stable, Impermeable Hexacyanoferrate Anolyte for Nonaqueous Redox Flow Batteries. ACS Energy Letters, 9(9), 4273-4279. https://doi.org/10.1021/acsenergylett.4c01351

@article{4cee27887a574d58bf2c99c19ab4d572,

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 = "Publisher Copyright: {\textcopyright} 2024 American Chemical Society",

year = "2024",

month = sep,

day = "13",

doi = "10.1021/acsenergylett.4c01351",

language = "English",

volume = "9",

pages = "4273--4279",

journal = "ACS Energy Letters",

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Zhao, Y, Bheemireddy, SR, Yue, D, Yu, Z, Uddin, MA, Liu, H, Li, Z, Fang, X, Lyu, X, Agarwal, G, Shi, Z, Robertson, LA, Cheng, L, Li, T, Assary, RS, Srinivasan, V, Babinec, SJ, Zhang, Z, Moore, JS, Shkrob, IA, Wei, X & Zhang, L 2024, 'Stable, Impermeable Hexacyanoferrate Anolyte for Nonaqueous Redox Flow Batteries', ACS Energy Letters, vol. 9, no. 9, pp. 4273-4279. https://doi.org/10.1021/acsenergylett.4c01351

TY - JOUR

T1 - Stable, Impermeable Hexacyanoferrate Anolyte for Nonaqueous Redox Flow Batteries

AU - Zhao, Yuyue

AU - Bheemireddy, Sambasiva R.

AU - Yue, Diqing

AU - Yu, Zhou

AU - Uddin, Mohammad Afsar

AU - Liu, Haoyu

AU - Li, Zhiguang

AU - Fang, Xiaoting

AU - Lyu, Xingyi

AU - Agarwal, Garvit

AU - Shi, Zhangxing

AU - Robertson, Lily A.

AU - Cheng, Lei

AU - Li, Tao

AU - Assary, Rajeev S.

AU - Srinivasan, Venkat

AU - Babinec, Susan J.

AU - Zhang, Zhengcheng

AU - Moore, Jeffrey S.

AU - Shkrob, Ilya A.

AU - Wei, Xiaoliang

AU - Zhang, Lu

PY - 2024/9/13

Y1 - 2024/9/13

N2 - 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.

AB - 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.

UR - https://www.scopus.com/pages/publications/85200646113

U2 - 10.1021/acsenergylett.4c01351

DO - 10.1021/acsenergylett.4c01351

M3 - Article

AN - SCOPUS:85200646113

SN - 2380-8195

VL - 9

SP - 4273

EP - 4279

JO - ACS Energy Letters

JF - ACS Energy Letters

IS - 9

ER -

Stable, Impermeable Hexacyanoferrate Anolyte for Nonaqueous Redox Flow Batteries

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