Mechanistic insights of cycling stability of ferrocene catholytes in aqueous redox flow batteries†

Jian Luo; Maowei Hu; Wenda Wu; Bing Yuan; T. Leo Liu

doi:10.1039/d1ee03251h

Mechanistic insights of cycling stability of ferrocene catholytes in aqueous redox flow batteries†

Jian Luo
, Maowei Hu
, Wenda Wu
, Bing Yuan
, T. Leo Liu

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

68 Scopus citations

Abstract

Water soluble ferrocene (Fc) derivatives are promising cathode materials for aqueous organic redox flow batteries (AORFBs) towards scalable energy storage. However, their structure-performance relationship and degradation mechanism in aqueous electrolytes remain unclear. Herein, physicochemical and electrochemical properties, battery performance, and degradation mechanisms of three Fc catholytes, (ferrocenylmethyl)trimethylammonium chloride (C₁-FcNCl), (2-ferrocenyl-ethyl)trimethylammonium chloride (C₂-FcNCl), and (3-ferrocenyl-propyl)trimethylammonium chloride (C₃-FcNCl) in pH neutral aqueous electrolytes were systemically investigated. UV-Vis and gas chromatography (GC) studies confirmed the thermal and photolytic C_x-Cp⁻ ligand dissociation decomposition pathways of both discharged and charged states of C₁-FcNCl and C₂-FcNCl catholytes. In contrast, in the case of the C₃-FcNCl catholyte, the electron-donating 3-(trimethylammonium)propyl group strengthens the coordination between the C₃-Cp⁻ ligand and the Fe³⁺ or Fe²⁺ center and thus mitigates the ligand-dissociation degradation. Consistently, the Fc electrolytes displayed cycling stability in both half-cell and full-cell flow batteries in the order of C₁-FcNCl < C₂-FcNCl < C₃-FcNCl.

Original language	English
Pages (from-to)	1315-1324
Number of pages	10
Journal	Energy and Environmental Science
Volume	15
Issue number	3
DOIs	https://doi.org/10.1039/d1ee03251h
State	Published - Feb 3 2022
Externally published	Yes

Funding

We thank National Science Foundation (Career Award, Grant No. 1847674) and Utah State University (faculty startup funds to Dr T. Leo Liu) for supporting this study. M. H. is grateful for China CSC Abroad Studying Fellowship to support her study at Utah State University. We acknowledge that the NMR studies are supported by NSF's MRI program (award number 1429195).

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title = "Mechanistic insights of cycling stability of ferrocene catholytes in aqueous redox flow batteries†",

abstract = "Water soluble ferrocene (Fc) derivatives are promising cathode materials for aqueous organic redox flow batteries (AORFBs) towards scalable energy storage. However, their structure-performance relationship and degradation mechanism in aqueous electrolytes remain unclear. Herein, physicochemical and electrochemical properties, battery performance, and degradation mechanisms of three Fc catholytes, (ferrocenylmethyl)trimethylammonium chloride (C1-FcNCl), (2-ferrocenyl-ethyl)trimethylammonium chloride (C2-FcNCl), and (3-ferrocenyl-propyl)trimethylammonium chloride (C3-FcNCl) in pH neutral aqueous electrolytes were systemically investigated. UV-Vis and gas chromatography (GC) studies confirmed the thermal and photolytic Cx-Cp− ligand dissociation decomposition pathways of both discharged and charged states of C1-FcNCl and C2-FcNCl catholytes. In contrast, in the case of the C3-FcNCl catholyte, the electron-donating 3-(trimethylammonium)propyl group strengthens the coordination between the C3-Cp− ligand and the Fe3+ or Fe2+ center and thus mitigates the ligand-dissociation degradation. Consistently, the Fc electrolytes displayed cycling stability in both half-cell and full-cell flow batteries in the order of C1-FcNCl < C2-FcNCl < C3-FcNCl.",

author = "Jian Luo and Maowei Hu and Wenda Wu and Bing Yuan and Liu, \{T. Leo\}",

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T1 - Mechanistic insights of cycling stability of ferrocene catholytes in aqueous redox flow batteries†

AU - Luo, Jian

AU - Hu, Maowei

AU - Wu, Wenda

AU - Yuan, Bing

AU - Liu, T. Leo

PY - 2022/2/3

Y1 - 2022/2/3

N2 - Water soluble ferrocene (Fc) derivatives are promising cathode materials for aqueous organic redox flow batteries (AORFBs) towards scalable energy storage. However, their structure-performance relationship and degradation mechanism in aqueous electrolytes remain unclear. Herein, physicochemical and electrochemical properties, battery performance, and degradation mechanisms of three Fc catholytes, (ferrocenylmethyl)trimethylammonium chloride (C1-FcNCl), (2-ferrocenyl-ethyl)trimethylammonium chloride (C2-FcNCl), and (3-ferrocenyl-propyl)trimethylammonium chloride (C3-FcNCl) in pH neutral aqueous electrolytes were systemically investigated. UV-Vis and gas chromatography (GC) studies confirmed the thermal and photolytic Cx-Cp− ligand dissociation decomposition pathways of both discharged and charged states of C1-FcNCl and C2-FcNCl catholytes. In contrast, in the case of the C3-FcNCl catholyte, the electron-donating 3-(trimethylammonium)propyl group strengthens the coordination between the C3-Cp− ligand and the Fe3+ or Fe2+ center and thus mitigates the ligand-dissociation degradation. Consistently, the Fc electrolytes displayed cycling stability in both half-cell and full-cell flow batteries in the order of C1-FcNCl < C2-FcNCl < C3-FcNCl.

AB - Water soluble ferrocene (Fc) derivatives are promising cathode materials for aqueous organic redox flow batteries (AORFBs) towards scalable energy storage. However, their structure-performance relationship and degradation mechanism in aqueous electrolytes remain unclear. Herein, physicochemical and electrochemical properties, battery performance, and degradation mechanisms of three Fc catholytes, (ferrocenylmethyl)trimethylammonium chloride (C1-FcNCl), (2-ferrocenyl-ethyl)trimethylammonium chloride (C2-FcNCl), and (3-ferrocenyl-propyl)trimethylammonium chloride (C3-FcNCl) in pH neutral aqueous electrolytes were systemically investigated. UV-Vis and gas chromatography (GC) studies confirmed the thermal and photolytic Cx-Cp− ligand dissociation decomposition pathways of both discharged and charged states of C1-FcNCl and C2-FcNCl catholytes. In contrast, in the case of the C3-FcNCl catholyte, the electron-donating 3-(trimethylammonium)propyl group strengthens the coordination between the C3-Cp− ligand and the Fe3+ or Fe2+ center and thus mitigates the ligand-dissociation degradation. Consistently, the Fc electrolytes displayed cycling stability in both half-cell and full-cell flow batteries in the order of C1-FcNCl < C2-FcNCl < C3-FcNCl.

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JO - Energy and Environmental Science

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IS - 3

ER -

Mechanistic insights of cycling stability of ferrocene catholytes in aqueous redox flow batteries†

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