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Title: A symmetric organic-based nonaqueous redox flow battery and its state of charge diagnostics by FTIR

Abstract

Redox flow batteries have shown outstanding promise for grid-scale energy storage to promote utilization of renewable energy and improve grid stability. Nonaqueous battery systems can potentially achieve high energy density because of their broad voltage window. In this paper, we report a new organic redox-active material for use in a nonaqueous redox flow battery, 2-phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide (PTIO) that has high solubility (>2.6 M) in organic solvents. PTIO exhibits electrochemically reversible disproportionation reactions and thus can serve as both anolyte and catholyte redox materials in a symmetric flow cell. The PTIO flow battery has a moderate cell voltage of ~1.7 V and shows good cyclability under both cyclic voltammetry and flow cell conditions. Moreover, we demonstrate that FTIR can offer accurate estimation of the PTIO concentration in electrolytes and determine the state of charge of the PTIO flow cell, which suggests FTIR potentially as a powerful online battery status sensor. In conclusion, this study is expected to inspire more insights in this under-addressed area of state of charge analysis aiming at operational safety and reliability of flow batteries.

Authors:
 [1];  [1];  [2];  [3];  [4];  [5];  [5]; ORCiD logo [6];  [1];  [1];  [1];  [7];  [3];  [4];  [4];  [8];  [1]
  1. Joint Center for Energy Storage Research (JCESR) (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  2. Joint Center for Energy Storage Research (JCESR) (United States); Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Chemical Engineering
  3. Joint Center for Energy Storage Research (JCESR) (United States); Univ. of Michigan, Ann Arbor, MI (United States)
  4. Joint Center for Energy Storage Research (JCESR) (United States); Univ. of Illinois Urbana-Champaign, Urbana, IL (United States)
  5. Joint Center for Energy Storage Research (JCESR) (United States); Argonne National Lab. (ANL), Lemont, IL (United States)
  6. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  7. Joint Center for Energy Storage Research (JCESR) (United States); United Technologies Research Center, East Hartford, CT (United States)
  8. Joint Center for Energy Storage Research (JCESR) (United States); Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
1254564
Report Number(s):
PNNL-SA-115896
Journal ID: ISSN 2050-7488; JMCAET; 48374; KC0208010
Grant/Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Volume: 4; Journal Issue: 15; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Environmental Molecular Sciences Laboratory

Citation Formats

Duan, Wentao, Vemuri, Rama Ses, Milshtein, Jarrod D., Laramie, Sydney, Dmello, Rylan D., Huang, Jinhua, Zhang, Lu, Hu, Dehong, Vijayakumar, M., Wang, Wei, Liu, Jun, Darling, Robert E., Thompson, Levi, Smith, Kyle C., Moore, Jeffrey S., Brushett, Fikile, and Wei, Xiaoliang. A symmetric organic-based nonaqueous redox flow battery and its state of charge diagnostics by FTIR. United States: N. p., 2016. Web. doi:10.1039/c6ta01177b.
Duan, Wentao, Vemuri, Rama Ses, Milshtein, Jarrod D., Laramie, Sydney, Dmello, Rylan D., Huang, Jinhua, Zhang, Lu, Hu, Dehong, Vijayakumar, M., Wang, Wei, Liu, Jun, Darling, Robert E., Thompson, Levi, Smith, Kyle C., Moore, Jeffrey S., Brushett, Fikile, & Wei, Xiaoliang. A symmetric organic-based nonaqueous redox flow battery and its state of charge diagnostics by FTIR. United States. https://doi.org/10.1039/c6ta01177b
Duan, Wentao, Vemuri, Rama Ses, Milshtein, Jarrod D., Laramie, Sydney, Dmello, Rylan D., Huang, Jinhua, Zhang, Lu, Hu, Dehong, Vijayakumar, M., Wang, Wei, Liu, Jun, Darling, Robert E., Thompson, Levi, Smith, Kyle C., Moore, Jeffrey S., Brushett, Fikile, and Wei, Xiaoliang. 2016. "A symmetric organic-based nonaqueous redox flow battery and its state of charge diagnostics by FTIR". United States. https://doi.org/10.1039/c6ta01177b. https://www.osti.gov/servlets/purl/1254564.
@article{osti_1254564,
title = {A symmetric organic-based nonaqueous redox flow battery and its state of charge diagnostics by FTIR},
author = {Duan, Wentao and Vemuri, Rama Ses and Milshtein, Jarrod D. and Laramie, Sydney and Dmello, Rylan D. and Huang, Jinhua and Zhang, Lu and Hu, Dehong and Vijayakumar, M. and Wang, Wei and Liu, Jun and Darling, Robert E. and Thompson, Levi and Smith, Kyle C. and Moore, Jeffrey S. and Brushett, Fikile and Wei, Xiaoliang},
abstractNote = {Redox flow batteries have shown outstanding promise for grid-scale energy storage to promote utilization of renewable energy and improve grid stability. Nonaqueous battery systems can potentially achieve high energy density because of their broad voltage window. In this paper, we report a new organic redox-active material for use in a nonaqueous redox flow battery, 2-phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide (PTIO) that has high solubility (>2.6 M) in organic solvents. PTIO exhibits electrochemically reversible disproportionation reactions and thus can serve as both anolyte and catholyte redox materials in a symmetric flow cell. The PTIO flow battery has a moderate cell voltage of ~1.7 V and shows good cyclability under both cyclic voltammetry and flow cell conditions. Moreover, we demonstrate that FTIR can offer accurate estimation of the PTIO concentration in electrolytes and determine the state of charge of the PTIO flow cell, which suggests FTIR potentially as a powerful online battery status sensor. In conclusion, this study is expected to inspire more insights in this under-addressed area of state of charge analysis aiming at operational safety and reliability of flow batteries.},
doi = {10.1039/c6ta01177b},
url = {https://www.osti.gov/biblio/1254564}, journal = {Journal of Materials Chemistry. A},
issn = {2050-7488},
number = 15,
volume = 4,
place = {United States},
year = {Thu Mar 10 00:00:00 EST 2016},
month = {Thu Mar 10 00:00:00 EST 2016}
}

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Works referenced in this record:

Electrical Energy Storage for the Grid: A Battery of Choices
journal, November 2011


Recent Progress in Redox Flow Battery Research and Development
journal, September 2012


Electrochemical Energy Storage for Green Grid
journal, May 2011


Progress in Flow Battery Research and Development
journal, June 2011


Redox flow batteries a review
journal, September 2011


Progress in redox flow batteries, remaining challenges and their applications in energy storage
journal, January 2012


Pathways to low-cost electrochemical energy storage: a comparison of aqueous and nonaqueous flow batteries
journal, January 2014


Nonaqueous redox-flow batteries: organic solvents, supporting electrolytes, and redox pairs
journal, January 2015


The Chemistry of Redox-Flow Batteries
journal, June 2015


Flow Batteries: Current Status and Trends
journal, September 2015


Application of Redox Non-Innocent Ligands to Non-Aqueous Flow Battery Electrolytes
journal, September 2013


Performance of a Non-Aqueous Vanadium Acetylacetonate Prototype Redox Flow Battery: Examination of Separators and Capacity Decay
journal, December 2014


Towards an all-copper redox flow battery based on a copper-containing ionic liquid
journal, January 2016


A polyoxometalate flow battery
journal, August 2013


An All-Organic Non-aqueous Lithium-Ion Redox Flow Battery
journal, June 2012


Radical Compatibility with Nonaqueous Electrolytes and Its Impact on an All-Organic Redox Flow Battery
journal, April 2015


Electrochemical Properties of an All-Organic Redox Flow Battery Using 2,2,6,6-Tetramethyl-1-Piperidinyloxy and N-Methylphthalimide
journal, January 2011


Liquid Catholyte Molecules for Nonaqueous Redox Flow Batteries
journal, November 2014


Semi-Solid Lithium Rechargeable Flow Battery
journal, May 2011


Polysulfide Flow Batteries Enabled by Percolating Nanoscale Conductor Networks
journal, March 2014


Impact of Redox-Active Polymer Molecular Weight on the Electrochemical Properties and Transport Across Porous Separators in Nonaqueous Solvents
journal, October 2014

  • Nagarjuna, Gavvalapalli; Hui, Jingshu; Cheng, Kevin J.
  • Journal of the American Chemical Society, Vol. 136, Issue 46, p. 16309-16316
  • https://doi.org/10.1021/ja508482e

A chemistry and material perspective on lithium redox flow batteries towards high-density electrical energy storage
journal, January 2015


A membrane-free lithium/polysulfide semi-liquid battery for large-scale energy storage
journal, January 2013


On the Way Toward Understanding Solution Chemistry of Lithium Polysulfides for High Energy Li-S Redox Flow Batteries
journal, April 2015


TEMPO-Based Catholyte for High-Energy Density Nonaqueous Redox Flow Batteries
journal, October 2014


Towards High-Performance Nonaqueous Redox Flow Electrolyte Via Ionic Modification of Active Species
journal, August 2014


Anthraquinone with tailored structure for a nonaqueous metal–organic redox flow battery
journal, January 2012


Anion-Tunable Properties and Electrochemical Performance of Functionalized Ferrocene Compounds
journal, September 2015


Sustainable Electrical Energy Storage through the Ferrocene/Ferrocenium Redox Reaction in Aprotic Electrolyte
journal, August 2014


Towards sustainable and versatile energy storage devices: an overview of organic electrode materials
journal, January 2013


Organic Electrode Materials for Rechargeable Lithium Batteries
journal, May 2012


A metal-free organic–inorganic aqueous flow battery
journal, January 2014


A Total Organic Aqueous Redox Flow Battery Employing a Low Cost and Sustainable Methyl Viologen Anolyte and 4-HO-TEMPO Catholyte
journal, December 2015


An Inexpensive Aqueous Flow Battery for Large-Scale Electrical Energy Storage Based on Water-Soluble Organic Redox Couples
journal, January 2014


An aqueous, polymer-based redox-flow battery using non-corrosive, safe and low-cost materials
journal, October 2015


Alkaline quinone flow battery
journal, September 2015


Transport Property Requirements for Flow Battery Separators
journal, July 2015


Vanadium Flow Battery for Energy Storage: Prospects and Challenges
journal, March 2013


Cost and performance model for redox flow batteries
journal, February 2014


In Situ X-ray Near-Edge Absorption Spectroscopy Investigation of the State of Charge of All-Vanadium Redox Flow Batteries
journal, September 2014


An on-line spectroscopic monitoring system for the electrolytes in vanadium redox flow batteries
journal, January 2015


State of charge monitoring methods for vanadium redox flow battery control
journal, October 2011


Determining Vanadium Concentrations Using the UV-Vis Response Method
journal, January 2015


Spectroscopic Measurement of State of Charge in Vanadium Flow Batteries with an Analytical Model of V IV -V V Absorbance
journal, September 2015


Nitronyl Nitroxide Radicals as Organic Memory Elements with Both n- and p-Type Properties
journal, April 2011


Multi-electron redox reaction of an organic radical cathode induced by a mesopore carbon network with nitroxide polymers
journal, January 2013


On the Benefits of a Symmetric Redox Flow Battery
journal, December 2015


Microporous separators for Fe/V redox flow batteries
journal, November 2012


Optimization studies on a Fe/Cr redox flow battery
journal, January 1992


A New Fe/V Redox Flow Battery Using a Sulfuric/Chloric Mixed-Acid Supporting Electrolyte
journal, February 2012


A tetradentate Ni(II) complex cation as a single redox couple for non-aqueous flow batteries
journal, June 2015


Degradation mechanisms in the non-aqueous vanadium acetylacetonate redox flow battery
journal, May 2012


In-situ investigation of vanadium ion transport in redox flow battery
journal, November 2012


Capacity Decay and Remediation of Nafion-based All-Vanadium Redox Flow Batteries
journal, December 2012


A subtractive approach to molecular engineering of dimethoxybenzene-based redox materials for non-aqueous flow batteries
journal, January 2015


Porous Polymeric Composite Separators for Redox Flow Batteries
journal, April 2015


Nanoporous Polytetrafluoroethylene/Silica Composite Separator as a High-Performance All-Vanadium Redox Flow Battery Membrane
journal, May 2013


Evolutionary Design of Low Molecular Weight Organic Anolyte Materials for Applications in Nonaqueous Redox Flow Batteries
journal, October 2015


High–energy density nonaqueous all redox flow lithium battery enabled with a polymeric membrane
journal, November 2015


Polysulfide-Blocking Microporous Polymer Membrane Tailored for Hybrid Li-Sulfur Flow Batteries
journal, August 2015


The Importance of Cell Geometry and Electrolyte Properties to the Cell Potential of Zn-Ce Hybrid Flow Batteries
journal, November 2015


Influence of architecture and material properties on vanadium redox flow battery performance
journal, January 2016


Works referencing / citing this record:

Liquid Quinones for Solvent-Free Redox Flow Batteries
journal, September 2017


Na 3 V 2 (PO 4 ) 3 as the Sole Solid Energy Storage Material for Redox Flow Sodium‐Ion Battery
journal, June 2019


Redox-Flow-Batterien: von metallbasierten zu organischen Aktivmaterialien
journal, November 2016


Redox-Flow Batteries: From Metals to Organic Redox-Active Materials
journal, November 2016


Macromolecular Design Strategies for Preventing Active-Material Crossover in Non-Aqueous All-Organic Redox-Flow Batteries
journal, January 2017


Aqueous Flow Batteries: Research and Development
journal, November 2018


FTIR study of the surface properties and tribological behaviors of plasma-modified UHMWPE and zirconia
journal, November 2018


A bipolar nitronyl nitroxide small molecule for an all-organic symmetric redox-flow battery
journal, January 2017


All-polymer particulate slurry batteries
journal, June 2019


Bioinspired, high-stability, nonaqueous redox flow battery electrolytes
journal, January 2017


Improved synthesis of N -ethyl-3,7-bis(trifluoromethyl)phenothiazine
journal, January 2020


Progress in the Design of Polyoxovanadate-Alkoxides as Charge Carriers for Nonaqueous Redox Flow Batteries
journal, March 2019


Redox targeting-based flow batteries
journal, August 2019


Understanding and Mitigating Capacity Fade in Aqueous Organic Redox Flow Batteries
journal, January 2018


Operando Spectroelectrochemical Characterization of a Highly Stable Bioinspired Redox Flow Battery Active Material
journal, January 2019


Critical Review—Experimental Diagnostics and Material Characterization Techniques Used on Redox Flow Batteries
journal, January 2018


A High Voltage Organic Redox Flow Battery with Redox Couples O 2 /Tetrabutylammonium Complex and Tris(4-bromophenyl)amine as Redox Active Species
journal, January 2018


Understanding and Mitigating Capacity Fade in Aqueous Organic Redox Flow Batteries
journal, April 2018


Macromolecular Design Strategies for Preventing Active-Material Crossover in Non-Aqueous All-Organic Redox-Flow Batteries
journal, January 2017