Designer Fluorescent Redoxmer Self-Reports Side Reactions in Nonaqueous Redox Flow Batteries

Lily A. Robertson; Ilya A. Shkrob; Zhiguang Li; Garvit Agarwal; Zhou Yu; Rajeev S. Assary; Lei Cheng; Lu Zhang; Zhengcheng Zhang

doi:10.1002/batt.202400597

Designer Fluorescent Redoxmer Self-Reports Side Reactions in Nonaqueous Redox Flow Batteries

Lily A. Robertson, Ilya A. Shkrob, Zhiguang Li, Garvit Agarwal, Zhou Yu, Rajeev S. Assary, Lei Cheng, Lu Zhang, Zhengcheng Zhang

Energy Storage & Conversion

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

Abstract

The state of health (SOH) is a critical measure for evaluating and predicting performance of redox flow batteries (RFBs). However, diagnosing SOH of RFBs is often challenging due to the overwhelming complexity of the electrolytes and associated electrochemical reactions. Designing active molecules or redoxmers that can autonomously exhibit property changes upon specific stimuli may provide a viable way for early diagnosis of SOH. Herein, a dimerized redoxmer, DGL-N-CH₃, was designed and synthesized by linking blue-green fluorescent monomers through a diglycolamide linker. While DGL-N-CH₃ still maintains similar electrochemical behavior and strong fluorescence, we observe a unique side reaction when cycling DGL-N-CH₃ in H-cells, which leads to a side product, NHCH₃-BzNSN via linker cleavage. Interestingly, NHCH₃-BzNSN also emits fluorescence but at a longer wavelength. By taking advantage of this unique fluorescent change that corresponds to the growth of NHCH₃-BzNSN, we successfully established the capacity decay of DGL-N-CH₃ H-cell cycling, exemplifying a proof-of-concept self-reporting redoxmer design towards in situ SOH monitoring.

Original language	English
Journal	Batteries and Supercaps
DOIs	https://doi.org/10.1002/batt.202400597
State	Accepted/In press - 2024

Funding

The research was financially supported by the Joint Center for Energy Storage Research (JCESR), an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences. 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\u2010AC02\u201006CH11357. The U.S. Government retains for itself, and others acting on its behalf, a paid\u2010up nonexclusive, irrevocable worldwide license in said article to reproduce, prepare derivative works, distribute copies to the public, and perform publicly and display publicly, by or on behalf of the Government. se of the Center for Nanoscale Materials, an Office of Science user facility, was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE\u2010AC02\u201006CH11357.

Keywords

Long-duration energy storage
Nonaqueous flow batteries
Redoxmers
Spectroscopy
State of health

Access to Document

10.1002/batt.202400597

Cite this

@article{f3a495f3c15d4bc990248ed9554ba423,

title = "Designer Fluorescent Redoxmer Self-Reports Side Reactions in Nonaqueous Redox Flow Batteries",

abstract = "The state of health (SOH) is a critical measure for evaluating and predicting performance of redox flow batteries (RFBs). However, diagnosing SOH of RFBs is often challenging due to the overwhelming complexity of the electrolytes and associated electrochemical reactions. Designing active molecules or redoxmers that can autonomously exhibit property changes upon specific stimuli may provide a viable way for early diagnosis of SOH. Herein, a dimerized redoxmer, DGL-N-CH3, was designed and synthesized by linking blue-green fluorescent monomers through a diglycolamide linker. While DGL-N-CH3 still maintains similar electrochemical behavior and strong fluorescence, we observe a unique side reaction when cycling DGL-N-CH3 in H-cells, which leads to a side product, NHCH3-BzNSN via linker cleavage. Interestingly, NHCH3-BzNSN also emits fluorescence but at a longer wavelength. By taking advantage of this unique fluorescent change that corresponds to the growth of NHCH3-BzNSN, we successfully established the capacity decay of DGL-N-CH3 H-cell cycling, exemplifying a proof-of-concept self-reporting redoxmer design towards in situ SOH monitoring.",

keywords = "Long-duration energy storage, Nonaqueous flow batteries, Redoxmers, Spectroscopy, State of health",

author = "Robertson, {Lily A.} and Shkrob, {Ilya A.} and Zhiguang Li and Garvit Agarwal and Zhou Yu and Assary, {Rajeev S.} and Lei Cheng and Lu Zhang and Zhengcheng Zhang",

note = "Publisher Copyright: {\textcopyright} 2024 UChicago Argonne, LLC, Operator of Argonne National Laboratory. Batteries & Supercaps published by Wiley-VCH GmbH.",

year = "2024",

doi = "10.1002/batt.202400597",

language = "English",

journal = "Batteries and Supercaps",

issn = "2566-6223",

publisher = "wiley",

}

TY - JOUR

T1 - Designer Fluorescent Redoxmer Self-Reports Side Reactions in Nonaqueous Redox Flow Batteries

AU - Robertson, Lily A.

AU - Shkrob, Ilya A.

AU - Li, Zhiguang

AU - Agarwal, Garvit

AU - Yu, Zhou

AU - Assary, Rajeev S.

AU - Cheng, Lei

AU - Zhang, Lu

AU - Zhang, Zhengcheng

PY - 2024

Y1 - 2024

N2 - The state of health (SOH) is a critical measure for evaluating and predicting performance of redox flow batteries (RFBs). However, diagnosing SOH of RFBs is often challenging due to the overwhelming complexity of the electrolytes and associated electrochemical reactions. Designing active molecules or redoxmers that can autonomously exhibit property changes upon specific stimuli may provide a viable way for early diagnosis of SOH. Herein, a dimerized redoxmer, DGL-N-CH3, was designed and synthesized by linking blue-green fluorescent monomers through a diglycolamide linker. While DGL-N-CH3 still maintains similar electrochemical behavior and strong fluorescence, we observe a unique side reaction when cycling DGL-N-CH3 in H-cells, which leads to a side product, NHCH3-BzNSN via linker cleavage. Interestingly, NHCH3-BzNSN also emits fluorescence but at a longer wavelength. By taking advantage of this unique fluorescent change that corresponds to the growth of NHCH3-BzNSN, we successfully established the capacity decay of DGL-N-CH3 H-cell cycling, exemplifying a proof-of-concept self-reporting redoxmer design towards in situ SOH monitoring.

AB - The state of health (SOH) is a critical measure for evaluating and predicting performance of redox flow batteries (RFBs). However, diagnosing SOH of RFBs is often challenging due to the overwhelming complexity of the electrolytes and associated electrochemical reactions. Designing active molecules or redoxmers that can autonomously exhibit property changes upon specific stimuli may provide a viable way for early diagnosis of SOH. Herein, a dimerized redoxmer, DGL-N-CH3, was designed and synthesized by linking blue-green fluorescent monomers through a diglycolamide linker. While DGL-N-CH3 still maintains similar electrochemical behavior and strong fluorescence, we observe a unique side reaction when cycling DGL-N-CH3 in H-cells, which leads to a side product, NHCH3-BzNSN via linker cleavage. Interestingly, NHCH3-BzNSN also emits fluorescence but at a longer wavelength. By taking advantage of this unique fluorescent change that corresponds to the growth of NHCH3-BzNSN, we successfully established the capacity decay of DGL-N-CH3 H-cell cycling, exemplifying a proof-of-concept self-reporting redoxmer design towards in situ SOH monitoring.

KW - Long-duration energy storage

KW - Nonaqueous flow batteries

KW - Redoxmers

KW - Spectroscopy

KW - State of health

UR - http://www.scopus.com/inward/record.url?scp=85212183912&partnerID=8YFLogxK

U2 - 10.1002/batt.202400597

DO - 10.1002/batt.202400597

M3 - Article

AN - SCOPUS:85212183912

SN - 2566-6223

JO - Batteries and Supercaps

JF - Batteries and Supercaps

ER -

Designer Fluorescent Redoxmer Self-Reports Side Reactions in Nonaqueous Redox Flow Batteries

Abstract

Funding

Keywords

Access to Document

Other files and links

Fingerprint

Cite this