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Title: Near Neutral pH Redox Flow Battery with Low Permeability and Long-Lifetime Phosphonated Viologen Active Species

Abstract

A highly stable phosphonate-functionalized viologen is introduced in this work as the redox-active material in a negative potential electrolyte for aqueous redox flow batteries (ARFBs) operating at nearly neutral pH. The solubility is 1.23 m and the reduction potential is the lowest of any substituted viologen utilized in a flow battery, reaching –0.462 V versus SHE at pH = 9. The negative charges in both the oxidized and the reduced states of 1,1'-bis(3-phosphonopropyl)-[4,4'-bipyridine]-1,1'-diium dibromide (BPP–Vi ) effect low permeability in cation exchange membranes and suppress a bimolecular mechanism of viologen decomposition. A flow battery pairing BPP–Vi with a ferrocyanide-based positive potential electrolyte across an inexpensive, non-fluorinated cation exchange membrane at pH = 9 exhibits an open-circuit voltage of 0.9 V and a capacity fade rate of 0.016% per day or 0.00069% per cycle. Overcharging leads to viologen decomposition, causing irreversible capacity fade. Our research introduces extremely stable, extremely low-permeating and low reduction potential redox active materials into near neutral ARFBs.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [2];  [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Harvard Univ., Cambridge, MA (United States). John A. Paulson School of Engineering and Applied Sciences
  2. Harvard Univ., Cambridge, MA (United States)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Harvard Univ., Cambridge, MA (United States)
Sponsoring Org.:
USDOE; National Science Foundation (NSF)
Contributing Org.:
Massachusetts Clean Energy Center
OSTI Identifier:
1608418
Alternate Identifier(s):
OSTI ID: 1608377
Grant/Contract Number:  
AC05-76RL01830; CBET‐1914543; 428977
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Energy Materials
Additional Journal Information:
Journal Volume: 10; Journal Issue: 20; Journal ID: ISSN 1614-6832
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; redox flow battery; viologen; low permeability; neutral pH

Citation Formats

Jin, Shijian, Fell, Eric M., Vina-Lopez, Lucia, Jing, Yan, Michalak, P. Winston, Gordon, Roy G., and Aziz, Michael J. Near Neutral pH Redox Flow Battery with Low Permeability and Long-Lifetime Phosphonated Viologen Active Species. United States: N. p., 2020. Web. doi:10.1002/aenm.202000100.
Jin, Shijian, Fell, Eric M., Vina-Lopez, Lucia, Jing, Yan, Michalak, P. Winston, Gordon, Roy G., & Aziz, Michael J. Near Neutral pH Redox Flow Battery with Low Permeability and Long-Lifetime Phosphonated Viologen Active Species. United States. doi:https://doi.org/10.1002/aenm.202000100
Jin, Shijian, Fell, Eric M., Vina-Lopez, Lucia, Jing, Yan, Michalak, P. Winston, Gordon, Roy G., and Aziz, Michael J. Mon . "Near Neutral pH Redox Flow Battery with Low Permeability and Long-Lifetime Phosphonated Viologen Active Species". United States. doi:https://doi.org/10.1002/aenm.202000100. https://www.osti.gov/servlets/purl/1608418.
@article{osti_1608418,
title = {Near Neutral pH Redox Flow Battery with Low Permeability and Long-Lifetime Phosphonated Viologen Active Species},
author = {Jin, Shijian and Fell, Eric M. and Vina-Lopez, Lucia and Jing, Yan and Michalak, P. Winston and Gordon, Roy G. and Aziz, Michael J.},
abstractNote = {A highly stable phosphonate-functionalized viologen is introduced in this work as the redox-active material in a negative potential electrolyte for aqueous redox flow batteries (ARFBs) operating at nearly neutral pH. The solubility is 1.23 m and the reduction potential is the lowest of any substituted viologen utilized in a flow battery, reaching –0.462 V versus SHE at pH = 9. The negative charges in both the oxidized and the reduced states of 1,1'-bis(3-phosphonopropyl)-[4,4'-bipyridine]-1,1'-diium dibromide (BPP–Vi ) effect low permeability in cation exchange membranes and suppress a bimolecular mechanism of viologen decomposition. A flow battery pairing BPP–Vi with a ferrocyanide-based positive potential electrolyte across an inexpensive, non-fluorinated cation exchange membrane at pH = 9 exhibits an open-circuit voltage of 0.9 V and a capacity fade rate of 0.016% per day or 0.00069% per cycle. Overcharging leads to viologen decomposition, causing irreversible capacity fade. Our research introduces extremely stable, extremely low-permeating and low reduction potential redox active materials into near neutral ARFBs.},
doi = {10.1002/aenm.202000100},
journal = {Advanced Energy Materials},
number = 20,
volume = 10,
place = {United States},
year = {2020},
month = {4}
}

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