Tailoring Two-Electron-Donating Phenothiazines to Enable High-Concentration Redox Electrolytes for Use in Nonaqueous Redox Flow Batteries

N. Harsha Attanayake; Jeffrey A. Kowalski; Katharine V. Greco; Matthew D. Casselman; Jarrod D. Milshtein; Steven J. Chapman; Sean R. Parkin; Fikile R. Brushett; Susan A. Odom

doi:10.1021/acs.chemmater.8b04770

Tailoring Two-Electron-Donating Phenothiazines to Enable High-Concentration Redox Electrolytes for Use in Nonaqueous Redox Flow Batteries

N. Harsha Attanayake, Jeffrey A. Kowalski, Katharine V. Greco, Matthew D. Casselman, Jarrod D. Milshtein, Steven J. Chapman, Sean R. Parkin, Fikile R. Brushett, Susan A. Odom

Chemistry

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

105 Scopus citations

Abstract

This study aims to advance our understanding of the physical and electrochemical behavior of nonaqueous redox electrolytes at elevated concentrations and to develop experimentally informed structure-property relationships that may ultimately enable deterministic design of soluble multielectron-transfer organic redox couples for use in redox flow batteries. To this end, we functionalized a phenothiazine core to simultaneously impart two desired properties: high solubility and multiple electron transfer. Specifically, we report the synthesis, solubility, and electrochemical analysis of two new phenothiazine derivatives, 3,7-dimethoxy-N-(2-(2-methoxyethoxy)ethyl)phenothiazine and N-ethyl-3,7-bis(2-(2-methoxyethoxy)ethoxy)phenothiazine, both of which are two-electron donors that are miscible with nonaqueous electrolytes. This dual-property improvement compared to previous phenothiazine derivatives allows for extended symmetric flow cell experiments for 460 h of cycling of a multielectron transfer system at high concentrations (0.3 M active material, 0.6 M faradaic concentration), better representing practical devices.

Original language	English
Pages (from-to)	4353-4363
Number of pages	11
Journal	Chemistry of Materials
Volume	31
Issue number	12
DOIs	https://doi.org/10.1021/acs.chemmater.8b04770
State	Published - Jun 25 2019

Bibliographical note

Publisher Copyright:
© Copyright 2019 American Chemical Society.

Funding

This work was funded by the National Science Foundation’s Division of Chemistry (award 1300653) and EPSCoR Program (award 1355438), and through the Department of Energy, Office of Basic Science through an Energy Innovation Hub: Joint Center for Energy Storage Research (JCESR). We thank Andrew Hipsley for assistance in the acquisition of EPR spectra. Crystallographic work was supported by the NSF MRI program (awards CHE-0319176 and CHE-1625732).

Funders	Funder number
National Science Foundation’s Division of Chemistry	1300653
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	CHE-0319176, 1701085, CHE-1625732
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
U.S. Department of Energy Oak Ridge National Laboratory U.S. Department of Energy National Science Foundation National Energy Research Scientific Computing Center
Office of Experimental Program to Stimulate Competitive Research	1355438
Office of Experimental Program to Stimulate Competitive Research

ASJC Scopus subject areas

General Chemistry
General Chemical Engineering
Materials Chemistry

Access to Document

10.1021/acs.chemmater.8b04770

Cite this

Attanayake, N. H., Kowalski, J. A., Greco, K. V., Casselman, M. D., Milshtein, J. D., Chapman, S. J., Parkin, S. R., Brushett, F. R., & Odom, S. A. (2019). Tailoring Two-Electron-Donating Phenothiazines to Enable High-Concentration Redox Electrolytes for Use in Nonaqueous Redox Flow Batteries. Chemistry of Materials, 31(12), 4353-4363. https://doi.org/10.1021/acs.chemmater.8b04770

@article{734744a59e444f98aab8930dcd82d644,

title = "Tailoring Two-Electron-Donating Phenothiazines to Enable High-Concentration Redox Electrolytes for Use in Nonaqueous Redox Flow Batteries",

abstract = "This study aims to advance our understanding of the physical and electrochemical behavior of nonaqueous redox electrolytes at elevated concentrations and to develop experimentally informed structure-property relationships that may ultimately enable deterministic design of soluble multielectron-transfer organic redox couples for use in redox flow batteries. To this end, we functionalized a phenothiazine core to simultaneously impart two desired properties: high solubility and multiple electron transfer. Specifically, we report the synthesis, solubility, and electrochemical analysis of two new phenothiazine derivatives, 3,7-dimethoxy-N-(2-(2-methoxyethoxy)ethyl)phenothiazine and N-ethyl-3,7-bis(2-(2-methoxyethoxy)ethoxy)phenothiazine, both of which are two-electron donors that are miscible with nonaqueous electrolytes. This dual-property improvement compared to previous phenothiazine derivatives allows for extended symmetric flow cell experiments for 460 h of cycling of a multielectron transfer system at high concentrations (0.3 M active material, 0.6 M faradaic concentration), better representing practical devices.",

author = "Attanayake, \{N. Harsha\} and Kowalski, \{Jeffrey A.\} and Greco, \{Katharine V.\} and Casselman, \{Matthew D.\} and Milshtein, \{Jarrod D.\} and Chapman, \{Steven J.\} and Parkin, \{Sean R.\} and Brushett, \{Fikile R.\} and Odom, \{Susan A.\}",

year = "2019",

month = jun,

day = "25",

doi = "10.1021/acs.chemmater.8b04770",

language = "English",

volume = "31",

pages = "4353--4363",

number = "12",

}

TY - JOUR

T1 - Tailoring Two-Electron-Donating Phenothiazines to Enable High-Concentration Redox Electrolytes for Use in Nonaqueous Redox Flow Batteries

AU - Attanayake, N. Harsha

AU - Kowalski, Jeffrey A.

AU - Greco, Katharine V.

AU - Casselman, Matthew D.

AU - Milshtein, Jarrod D.

AU - Chapman, Steven J.

AU - Parkin, Sean R.

AU - Brushett, Fikile R.

AU - Odom, Susan A.

PY - 2019/6/25

Y1 - 2019/6/25

N2 - This study aims to advance our understanding of the physical and electrochemical behavior of nonaqueous redox electrolytes at elevated concentrations and to develop experimentally informed structure-property relationships that may ultimately enable deterministic design of soluble multielectron-transfer organic redox couples for use in redox flow batteries. To this end, we functionalized a phenothiazine core to simultaneously impart two desired properties: high solubility and multiple electron transfer. Specifically, we report the synthesis, solubility, and electrochemical analysis of two new phenothiazine derivatives, 3,7-dimethoxy-N-(2-(2-methoxyethoxy)ethyl)phenothiazine and N-ethyl-3,7-bis(2-(2-methoxyethoxy)ethoxy)phenothiazine, both of which are two-electron donors that are miscible with nonaqueous electrolytes. This dual-property improvement compared to previous phenothiazine derivatives allows for extended symmetric flow cell experiments for 460 h of cycling of a multielectron transfer system at high concentrations (0.3 M active material, 0.6 M faradaic concentration), better representing practical devices.

AB - This study aims to advance our understanding of the physical and electrochemical behavior of nonaqueous redox electrolytes at elevated concentrations and to develop experimentally informed structure-property relationships that may ultimately enable deterministic design of soluble multielectron-transfer organic redox couples for use in redox flow batteries. To this end, we functionalized a phenothiazine core to simultaneously impart two desired properties: high solubility and multiple electron transfer. Specifically, we report the synthesis, solubility, and electrochemical analysis of two new phenothiazine derivatives, 3,7-dimethoxy-N-(2-(2-methoxyethoxy)ethyl)phenothiazine and N-ethyl-3,7-bis(2-(2-methoxyethoxy)ethoxy)phenothiazine, both of which are two-electron donors that are miscible with nonaqueous electrolytes. This dual-property improvement compared to previous phenothiazine derivatives allows for extended symmetric flow cell experiments for 460 h of cycling of a multielectron transfer system at high concentrations (0.3 M active material, 0.6 M faradaic concentration), better representing practical devices.

UR - https://www.scopus.com/pages/publications/85067069866

UR - https://www.scopus.com/inward/citedby.url?scp=85067069866&partnerID=8YFLogxK

U2 - 10.1021/acs.chemmater.8b04770

DO - 10.1021/acs.chemmater.8b04770

M3 - Article

AN - SCOPUS:85067069866

SN - 0897-4756

VL - 31

SP - 4353

EP - 4363

JO - Chemistry of Materials

JF - Chemistry of Materials

IS - 12

ER -

Tailoring Two-Electron-Donating Phenothiazines to Enable High-Concentration Redox Electrolytes for Use in Nonaqueous Redox Flow Batteries

Abstract

Bibliographical note

Funding

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this