Mitigating Ring-Opening to Develop Stable TEMPO Catholytes for pH-Neutral All-Organic Redox Flow Batteries

Hao Fan; Wenda Wu; Mahalingam Ravivarma; Hongbin Li; Bo Hu; Jiafeng Lei; Yangyang Feng; Xiaohua Sun; Jiangxuan Song; Tianbiao Leo Liu

doi:10.1002/adfm.202203032

Mitigating Ring-Opening to Develop Stable TEMPO Catholytes for pH-Neutral All-Organic Redox Flow Batteries

Hao Fan
, Wenda Wu
, Mahalingam Ravivarma
, Hongbin Li
, Bo Hu
, Jiafeng Lei
, Yangyang Feng
, Xiaohua Sun
, Jiangxuan Song
, Tianbiao Leo Liu

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

54 Scopus citations

Abstract

Redox-active organics are highly attractive in aqueous organic redox flow batteries (AORFBs). However, the lack of capacity dense, stable organic catholytes remains a challenge to develop energy-dense, long cycle-life AORFBs. Herein, a stable organic catholyte, 4-[3-(trimethylammonium)acetylamino]-2,2,6,6-tetramethylpiperidine-1-oxyl chloride (TMAAcNHTEMPO) is developed through rational molecular engineering using connective acetamido and trimethylammonium groups. Paired with bis-(trimethylammonium) propyl viologen tetrachloride anolyte, stable AORFBs (up to 1500 cycles) with a low capacity fade rate of ca. 0.0144% h⁻¹ are achieved. Experimental characterizations and theoretical simulations revealed that TMAAcNH-TEMPO is largely stabilized by the reduced reactivity of the nitroxyl radical moiety that mitigates a ring-opening side reaction.

Original language	English
Article number	2203032
Journal	Advanced Functional Materials
Volume	32
Issue number	33
DOIs	https://doi.org/10.1002/adfm.202203032
State	Published - Aug 15 2022
Externally published	Yes

Funding

This study was financially supported by grants from the National Natural Science Foundation of China (Nos. 21875181), Natural Science Basic Research Program of Shaanxi (Program No. 2019JLP‐13), Shaanxi Key Research and Development Project (No. 2019TSLGY07‐05) and 111 Project 2.0 (BP2018008). T. Leo Liu and Wenda Wu 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. Xiaohua Sun acknowledges the support by the 111 Project of the Ministry of Education of China (D20015).The authors would like to thank Ying Zhang, and Gang Chang at the Instrument Analysis Center of Xi'an Jiaotong University for the assistance of ESI‐MS and NMR analyses. The authors would like to thank Lijing Ma at the State Key Laboratory of Multiphase Flow in Power Engineering of Xi'an Jiaotong University for the assistance of EPR measurements. This study was financially supported by grants from the National Natural Science Foundation of China (Nos. 21875181), Natural Science Basic Research Program of Shaanxi (Program No. 2019JLP-13), Shaanxi Key Research and Development Project (No. 2019TSLGY07-05) and 111 Project 2.0 (BP2018008). T. Leo Liu and Wenda Wu 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. Xiaohua Sun acknowledges the support by the 111 Project of the Ministry of Education of China (D20015).The authors would like to thank Ying Zhang, and Gang Chang at the Instrument Analysis Center of Xi'an Jiaotong University for the assistance of ESI-MS and NMR analyses. The authors would like to thank Lijing Ma at the State Key Laboratory of Multiphase Flow in Power Engineering of Xi'an Jiaotong University for the assistance of EPR measurements.

Keywords

energy storage
nitroxyl radicals
organic catholytes
redox flow batteries

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10.1002/adfm.202203032

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title = "Mitigating Ring-Opening to Develop Stable TEMPO Catholytes for pH-Neutral All-Organic Redox Flow Batteries",

abstract = "Redox-active organics are highly attractive in aqueous organic redox flow batteries (AORFBs). However, the lack of capacity dense, stable organic catholytes remains a challenge to develop energy-dense, long cycle-life AORFBs. Herein, a stable organic catholyte, 4-[3-(trimethylammonium)acetylamino]-2,2,6,6-tetramethylpiperidine-1-oxyl chloride (TMAAcNHTEMPO) is developed through rational molecular engineering using connective acetamido and trimethylammonium groups. Paired with bis-(trimethylammonium) propyl viologen tetrachloride anolyte, stable AORFBs (up to 1500 cycles) with a low capacity fade rate of ca. 0.0144\% h−1 are achieved. Experimental characterizations and theoretical simulations revealed that TMAAcNH-TEMPO is largely stabilized by the reduced reactivity of the nitroxyl radical moiety that mitigates a ring-opening side reaction.",

keywords = "energy storage, nitroxyl radicals, organic catholytes, redox flow batteries",

author = "Hao Fan and Wenda Wu and Mahalingam Ravivarma and Hongbin Li and Bo Hu and Jiafeng Lei and Yangyang Feng and Xiaohua Sun and Jiangxuan Song and Liu, \{Tianbiao Leo\}",

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year = "2022",

month = aug,

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doi = "10.1002/adfm.202203032",

language = "English",

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T1 - Mitigating Ring-Opening to Develop Stable TEMPO Catholytes for pH-Neutral All-Organic Redox Flow Batteries

AU - Fan, Hao

AU - Wu, Wenda

AU - Ravivarma, Mahalingam

AU - Li, Hongbin

AU - Hu, Bo

AU - Lei, Jiafeng

AU - Feng, Yangyang

AU - Sun, Xiaohua

AU - Song, Jiangxuan

AU - Liu, Tianbiao Leo

PY - 2022/8/15

Y1 - 2022/8/15

N2 - Redox-active organics are highly attractive in aqueous organic redox flow batteries (AORFBs). However, the lack of capacity dense, stable organic catholytes remains a challenge to develop energy-dense, long cycle-life AORFBs. Herein, a stable organic catholyte, 4-[3-(trimethylammonium)acetylamino]-2,2,6,6-tetramethylpiperidine-1-oxyl chloride (TMAAcNHTEMPO) is developed through rational molecular engineering using connective acetamido and trimethylammonium groups. Paired with bis-(trimethylammonium) propyl viologen tetrachloride anolyte, stable AORFBs (up to 1500 cycles) with a low capacity fade rate of ca. 0.0144% h−1 are achieved. Experimental characterizations and theoretical simulations revealed that TMAAcNH-TEMPO is largely stabilized by the reduced reactivity of the nitroxyl radical moiety that mitigates a ring-opening side reaction.

AB - Redox-active organics are highly attractive in aqueous organic redox flow batteries (AORFBs). However, the lack of capacity dense, stable organic catholytes remains a challenge to develop energy-dense, long cycle-life AORFBs. Herein, a stable organic catholyte, 4-[3-(trimethylammonium)acetylamino]-2,2,6,6-tetramethylpiperidine-1-oxyl chloride (TMAAcNHTEMPO) is developed through rational molecular engineering using connective acetamido and trimethylammonium groups. Paired with bis-(trimethylammonium) propyl viologen tetrachloride anolyte, stable AORFBs (up to 1500 cycles) with a low capacity fade rate of ca. 0.0144% h−1 are achieved. Experimental characterizations and theoretical simulations revealed that TMAAcNH-TEMPO is largely stabilized by the reduced reactivity of the nitroxyl radical moiety that mitigates a ring-opening side reaction.

KW - energy storage

KW - nitroxyl radicals

KW - organic catholytes

KW - redox flow batteries

UR - https://www.scopus.com/pages/publications/85131576010

U2 - 10.1002/adfm.202203032

DO - 10.1002/adfm.202203032

M3 - Article

AN - SCOPUS:85131576010

SN - 1616-301X

VL - 32

JO - Advanced Functional Materials

JF - Advanced Functional Materials

IS - 33

M1 - 2203032

ER -

Mitigating Ring-Opening to Develop Stable TEMPO Catholytes for pH-Neutral All-Organic Redox Flow Batteries

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