High current density, long duration cycling of soluble organic active species for non-aqueous redox flow batteries

Jarrod D. Milshtein; Aman Preet Kaur; Matthew D. Casselman; Jeffrey A. Kowalski; Subrahmanyam Modekrutti; Peter L. Zhang; N. Harsha Attanayake; Corrine F. Elliott; Sean R. Parkin; Chad Risko; Fikile R. Brushett; Susan A. Odom

doi:10.1039/c6ee02027e

High current density, long duration cycling of soluble organic active species for non-aqueous redox flow batteries

Jarrod D. Milshtein, Aman Preet Kaur, Matthew D. Casselman, Jeffrey A. Kowalski, Subrahmanyam Modekrutti, Peter L. Zhang, N. Harsha Attanayake, Corrine F. Elliott, Sean R. Parkin, Chad Risko, Fikile R. Brushett, Susan A. Odom

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

210 Scopus citations

Abstract

Non-aqueous redox flow batteries (NAqRFBs) employing redox-active organic molecules show promise to meet requirements for grid energy storage. Here, we combine the rational design of organic molecules with flow cell engineering to boost NAqRFB performance. We synthesize two highly soluble phenothiazine derivatives, N-(2-methoxyethyl)phenothiazine (MEPT) and N-[2-(2-methoxyethoxy)ethyl]phenothiazine (MEEPT), via a one-step synthesis from inexpensive precursors. Synthesis and isolation of the radical-cation salts permit UV-vis decay studies that illustrate the high stability of these open-shell species. Cyclic voltammetry and bulk electrolysis experiments reveal the promising electrochemical properties of MEPT and MEEPT under dilute conditions. A high performance non-aqueous flow cell, employing interdigitated flow fields and carbon paper electrodes, is engineered and demonstrated; polarization and impedance studies quantify the cell's low area-specific resistance (3.2-3.3 Ω cm²). We combine the most soluble derivative, MEEPT, and its tetrafluoroborate radical-cation salt in the flow cell for symmetric cycling, evincing a current density of 100 mA cm^-2 with undetectable capacity fade over 100 cycles. This coincident high current density and capacity retention is unprecedented in NAqRFB literature.

Original language	English
Pages (from-to)	3531-3543
Number of pages	13
Journal	Energy and Environmental Science
Volume	9
Issue number	11
DOIs	https://doi.org/10.1039/c6ee02027e
State	Published - Nov 2016

Bibliographical note

Publisher Copyright:
© The Royal Society of Chemistry 2016.

Funding

Molecular synthesis and characterization studies were supported by the National Science Foundation (NSF), Division of Chemistry under Award Number CHE-1300653 and through the Experimental Program to Stimulate Competitive Research (EPSCoR) Award Number 1355438. Bulk electrolysis and flow cell studies were supported as part of 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. SAO and CR thank the University of Kentucky for start-up funds. JDM acknowledges additional financial support from the NSF Graduate Research Fellowship Program (DGE 1256260). The authors thank Daramic for providing samples of battery separators.

Funders	Funder number
U.S. Department of Energy Chinese Academy of Sciences Guangzhou Municipal Science and Technology Project Oak Ridge National Laboratory Extreme Science and Engineering Discovery Environment National Science Foundation National Energy Research Scientific Computing Center National Natural Science Foundation of China
DOE Basic Energy Sciences
U.S. Department of Energy Oak Ridge National Laboratory U.S. Department of Energy National Science Foundation National Energy Research Scientific Computing Center
National Science Foundation Office of International Science and Engineering
Office of Experimental Program to Stimulate Competitive Research	1355438
Department of Chemistry and Division of Medicinal Chemistry and Pharmaceutics	CHE-1300653
University of Kentucky	DGE 1256260

ASJC Scopus subject areas

Environmental Chemistry
Renewable Energy, Sustainability and the Environment
Nuclear Energy and Engineering
Pollution

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1039/c6ee02027e

Cite this

Milshtein, J. D., Kaur, A. P., Casselman, M. D., Kowalski, J. A., Modekrutti, S., Zhang, P. L., Harsha Attanayake, N., Elliott, C. F., Parkin, S. R., Risko, C., Brushett, F. R., & Odom, S. A. (2016). High current density, long duration cycling of soluble organic active species for non-aqueous redox flow batteries. Energy and Environmental Science, 9(11), 3531-3543. https://doi.org/10.1039/c6ee02027e

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title = "High current density, long duration cycling of soluble organic active species for non-aqueous redox flow batteries",

abstract = "Non-aqueous redox flow batteries (NAqRFBs) employing redox-active organic molecules show promise to meet requirements for grid energy storage. Here, we combine the rational design of organic molecules with flow cell engineering to boost NAqRFB performance. We synthesize two highly soluble phenothiazine derivatives, N-(2-methoxyethyl)phenothiazine (MEPT) and N-[2-(2-methoxyethoxy)ethyl]phenothiazine (MEEPT), via a one-step synthesis from inexpensive precursors. Synthesis and isolation of the radical-cation salts permit UV-vis decay studies that illustrate the high stability of these open-shell species. Cyclic voltammetry and bulk electrolysis experiments reveal the promising electrochemical properties of MEPT and MEEPT under dilute conditions. A high performance non-aqueous flow cell, employing interdigitated flow fields and carbon paper electrodes, is engineered and demonstrated; polarization and impedance studies quantify the cell's low area-specific resistance (3.2-3.3 Ω cm2). We combine the most soluble derivative, MEEPT, and its tetrafluoroborate radical-cation salt in the flow cell for symmetric cycling, evincing a current density of 100 mA cm-2 with undetectable capacity fade over 100 cycles. This coincident high current density and capacity retention is unprecedented in NAqRFB literature.",

author = "Milshtein, \{Jarrod D.\} and Kaur, \{Aman Preet\} and Casselman, \{Matthew D.\} and Kowalski, \{Jeffrey A.\} and Subrahmanyam Modekrutti and Zhang, \{Peter L.\} and \{Harsha Attanayake\}, N. and Elliott, \{Corrine F.\} and Parkin, \{Sean R.\} and Chad Risko and Brushett, \{Fikile R.\} and Odom, \{Susan A.\}",

note = "Publisher Copyright: {\textcopyright} The Royal Society of Chemistry 2016.",

year = "2016",

month = nov,

doi = "10.1039/c6ee02027e",

language = "English",

volume = "9",

pages = "3531--3543",

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Milshtein, JD, Kaur, AP, Casselman, MD, Kowalski, JA, Modekrutti, S, Zhang, PL, Harsha Attanayake, N, Elliott, CF, Parkin, SR, Risko, C, Brushett, FR & Odom, SA 2016, 'High current density, long duration cycling of soluble organic active species for non-aqueous redox flow batteries', Energy and Environmental Science, vol. 9, no. 11, pp. 3531-3543. https://doi.org/10.1039/c6ee02027e

TY - JOUR

T1 - High current density, long duration cycling of soluble organic active species for non-aqueous redox flow batteries

AU - Milshtein, Jarrod D.

AU - Kaur, Aman Preet

AU - Casselman, Matthew D.

AU - Kowalski, Jeffrey A.

AU - Modekrutti, Subrahmanyam

AU - Zhang, Peter L.

AU - Harsha Attanayake, N.

AU - Elliott, Corrine F.

AU - Parkin, Sean R.

AU - Risko, Chad

AU - Brushett, Fikile R.

AU - Odom, Susan A.

PY - 2016/11

Y1 - 2016/11

N2 - Non-aqueous redox flow batteries (NAqRFBs) employing redox-active organic molecules show promise to meet requirements for grid energy storage. Here, we combine the rational design of organic molecules with flow cell engineering to boost NAqRFB performance. We synthesize two highly soluble phenothiazine derivatives, N-(2-methoxyethyl)phenothiazine (MEPT) and N-[2-(2-methoxyethoxy)ethyl]phenothiazine (MEEPT), via a one-step synthesis from inexpensive precursors. Synthesis and isolation of the radical-cation salts permit UV-vis decay studies that illustrate the high stability of these open-shell species. Cyclic voltammetry and bulk electrolysis experiments reveal the promising electrochemical properties of MEPT and MEEPT under dilute conditions. A high performance non-aqueous flow cell, employing interdigitated flow fields and carbon paper electrodes, is engineered and demonstrated; polarization and impedance studies quantify the cell's low area-specific resistance (3.2-3.3 Ω cm2). We combine the most soluble derivative, MEEPT, and its tetrafluoroborate radical-cation salt in the flow cell for symmetric cycling, evincing a current density of 100 mA cm-2 with undetectable capacity fade over 100 cycles. This coincident high current density and capacity retention is unprecedented in NAqRFB literature.

AB - Non-aqueous redox flow batteries (NAqRFBs) employing redox-active organic molecules show promise to meet requirements for grid energy storage. Here, we combine the rational design of organic molecules with flow cell engineering to boost NAqRFB performance. We synthesize two highly soluble phenothiazine derivatives, N-(2-methoxyethyl)phenothiazine (MEPT) and N-[2-(2-methoxyethoxy)ethyl]phenothiazine (MEEPT), via a one-step synthesis from inexpensive precursors. Synthesis and isolation of the radical-cation salts permit UV-vis decay studies that illustrate the high stability of these open-shell species. Cyclic voltammetry and bulk electrolysis experiments reveal the promising electrochemical properties of MEPT and MEEPT under dilute conditions. A high performance non-aqueous flow cell, employing interdigitated flow fields and carbon paper electrodes, is engineered and demonstrated; polarization and impedance studies quantify the cell's low area-specific resistance (3.2-3.3 Ω cm2). We combine the most soluble derivative, MEEPT, and its tetrafluoroborate radical-cation salt in the flow cell for symmetric cycling, evincing a current density of 100 mA cm-2 with undetectable capacity fade over 100 cycles. This coincident high current density and capacity retention is unprecedented in NAqRFB literature.

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DO - 10.1039/c6ee02027e

M3 - Article

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SN - 1754-5692

VL - 9

SP - 3531

EP - 3543

JO - Energy and Environmental Science

JF - Energy and Environmental Science

IS - 11

ER -

High current density, long duration cycling of soluble organic active species for non-aqueous redox flow batteries

Abstract

Bibliographical note

Funding

ASJC Scopus subject areas

UN SDGs

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