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Title: Understanding the Role of Complexation in the Charge-Transfer Kinetics of the Cu 2+ + e ↔ Cu 1+ Redox Reaction in Ethaline Deep Eutectic Solvent

Abstract

Deep eutectic solvent (DES) based electrolytes are gaining attention for electrochemical applications. As such, knowledge of the charge transfer kinetics in DES and its dependence on electrolyte composition and temperature is important. Using Cu 2+ + e ↔ Cu 1+ as a model system, we demonstrate that metal redox reactions in chloride-containing DES media suffer from sluggish charge transfer kinetics. The exchange current density, i 0, displayed a peculiar inverse relationship with the bulk chloride concentration, [Cl ] b. The i 0 decreased from 7.9 to 3.0 mA/cm 2 when [Cl ] b increased from 2.8 to 4.6 M at 30°C. Such dependence is shown to originate from Cl complexation with reactant and product species. Furthermore, i 0 increased with an increase in Cu n+ bulk concentration in the 50–200 mM range. Also, increase in temperature elevated i 0. The charge transfer coefficient α c, however, remained constant (~0.5) and was unaffected by Cu n+ or Cl concentrations or by temperature. To explain how charge transfer kinetics depend on the various system parameters, a model incorporating complexation phenomena was developed and its predictions were compared to experiments.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Case Western Reserve Univ., Cleveland, OH (United States). Dept. of Chemical and Biomolecular Engineering
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Div.
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1574915
Report Number(s):
BNL-212339-2019-JAAM
Journal ID: ISSN 0013-4651
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 166; Journal Issue: 15; Journal ID: ISSN 0013-4651
Publisher:
The Electrochemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; Electrochemical Engineering; Electrodeposition - Copper; Complexation; Deep eutectic solvent; Electrochemical redox reactions

Citation Formats

Shen, Dai, Vukmirovic, Miomir B., and Akolkar, Rohan. Understanding the Role of Complexation in the Charge-Transfer Kinetics of the Cu2+ + e ↔ Cu1+ Redox Reaction in Ethaline Deep Eutectic Solvent. United States: N. p., 2019. Web. doi:10.1149/2.1211915jes.
Shen, Dai, Vukmirovic, Miomir B., & Akolkar, Rohan. Understanding the Role of Complexation in the Charge-Transfer Kinetics of the Cu2+ + e ↔ Cu1+ Redox Reaction in Ethaline Deep Eutectic Solvent. United States. doi:10.1149/2.1211915jes.
Shen, Dai, Vukmirovic, Miomir B., and Akolkar, Rohan. Fri . "Understanding the Role of Complexation in the Charge-Transfer Kinetics of the Cu2+ + e ↔ Cu1+ Redox Reaction in Ethaline Deep Eutectic Solvent". United States. doi:10.1149/2.1211915jes. https://www.osti.gov/servlets/purl/1574915.
@article{osti_1574915,
title = {Understanding the Role of Complexation in the Charge-Transfer Kinetics of the Cu2+ + e ↔ Cu1+ Redox Reaction in Ethaline Deep Eutectic Solvent},
author = {Shen, Dai and Vukmirovic, Miomir B. and Akolkar, Rohan},
abstractNote = {Deep eutectic solvent (DES) based electrolytes are gaining attention for electrochemical applications. As such, knowledge of the charge transfer kinetics in DES and its dependence on electrolyte composition and temperature is important. Using Cu2+ + e ↔ Cu1+ as a model system, we demonstrate that metal redox reactions in chloride-containing DES media suffer from sluggish charge transfer kinetics. The exchange current density, i0, displayed a peculiar inverse relationship with the bulk chloride concentration, [Cl–]b. The i0 decreased from 7.9 to 3.0 mA/cm2 when [Cl–]b increased from 2.8 to 4.6 M at 30°C. Such dependence is shown to originate from Cl– complexation with reactant and product species. Furthermore, i0 increased with an increase in Cun+ bulk concentration in the 50–200 mM range. Also, increase in temperature elevated i0. The charge transfer coefficient αc, however, remained constant (~0.5) and was unaffected by Cun+ or Cl– concentrations or by temperature. To explain how charge transfer kinetics depend on the various system parameters, a model incorporating complexation phenomena was developed and its predictions were compared to experiments.},
doi = {10.1149/2.1211915jes},
journal = {Journal of the Electrochemical Society},
number = 15,
volume = 166,
place = {United States},
year = {2019},
month = {11}
}

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Works referenced in this record:

The development of an all copper hybrid redox flow battery using deep eutectic solvents
journal, June 2013


Prospects of applying ionic liquids and deep eutectic solvents for renewable energy storage by means of redox flow batteries
journal, February 2014

  • Chakrabarti, Mohammed Harun; Mjalli, Farouq Sabri; AlNashef, Inas Muen
  • Renewable and Sustainable Energy Reviews, Vol. 30
  • DOI: 10.1016/j.rser.2013.10.004

A green and cost-effective rechargeable battery with high energy density based on a deep eutectic catholyte
journal, January 2016

  • Wang, Yarong; Zhou, Haoshen
  • Energy & Environmental Science, Vol. 9, Issue 7
  • DOI: 10.1039/C6EE00902F

Deep Eutectic Solvents: Physicochemical Properties and Gas Separation Applications
journal, March 2015

  • García, Gregorio; Aparicio, Santiago; Ullah, Ruh
  • Energy & Fuels, Vol. 29, Issue 4
  • DOI: 10.1021/ef5028873

Deep eutectic solvents: syntheses, properties and applications
journal, January 2012

  • Zhang, Qinghua; De Oliveira Vigier, Karine; Royer, Sébastien
  • Chemical Society Reviews, Vol. 41, Issue 21
  • DOI: 10.1039/c2cs35178a

Deep Eutectic Solvents (DESs) and Their Applications
journal, October 2014

  • Smith, Emma L.; Abbott, Andrew P.; Ryder, Karl S.
  • Chemical Reviews, Vol. 114, Issue 21
  • DOI: 10.1021/cr300162p

A non-aqueous all-copper redox flow battery with highly soluble active species
journal, May 2017


The Effect of Temperature on Kinetics and Diffusion Coefficients of Metallocene Derivatives in Polyol-Based Deep Eutectic Solvents
journal, December 2015


Electrochemical and transport properties of ethaline containing copper and tin chloride
journal, December 2013


Deep eutectic solvents based on choline chloride and ethylene glycol as media for extractive denitrification/desulfurization/dearomatization of motor fuels
journal, April 2019

  • Rogošić, Marko; Kučan, Kristina Zagajski
  • Journal of Industrial and Engineering Chemistry, Vol. 72
  • DOI: 10.1016/j.jiec.2018.12.006

Electrodeposition of copper composites from deep eutectic solvents based on choline chloride
journal, January 2009

  • Abbott, Andrew P.; El Ttaib, Khalid; Frisch, Gero
  • Physical Chemistry Chemical Physics, Vol. 11, Issue 21
  • DOI: 10.1039/b817881j

Electrochemical copper deposition from an ethaline-CuCl2·2H2O DES
journal, January 2014


The kinetics of the Cu2+/Cu+ redox couple in deep eutectic solvents
journal, May 2011


A kinetic study of the Cu(II)/Cu(I) system in Cl? media at the glassy carbon electrode
journal, January 1981

  • Kiekens, P.; Verbeeck, R. M. H.; Temmerman, E.
  • Mikrochimica Acta, Vol. 76, Issue 1-2
  • DOI: 10.1007/BF01197301

Avoiding Pitfalls in the Determination of Reliable Electrochemical Kinetics Parameters for the Cu 2+ → Cu 1+ Reduction Reaction in Deep Eutectic Solvents
journal, January 2018

  • Shen, Dai; Steinberg, Katherine; Akolkar, Rohan
  • Journal of The Electrochemical Society, Vol. 165, Issue 14
  • DOI: 10.1149/2.1011814jes

Speciation and reduction potentials of metal ions in concentrated chloride and sulfate solutions relevant to processing base metal sulfides
journal, February 1988

  • Senanayake, G.; Muir, D. M.
  • Metallurgical Transactions B, Vol. 19, Issue 1
  • DOI: 10.1007/BF02666488

Speciation of Copper(II) Complexes in an Ionic Liquid Based on Choline Chloride and in Choline Chloride/Water Mixtures
journal, April 2012

  • De Vreese, Peter; Brooks, Neil R.; Van Hecke, Kristof
  • Inorganic Chemistry, Vol. 51, Issue 9
  • DOI: 10.1021/ic202341m

EXAFS Study into the Speciation of Metal Salts Dissolved in Ionic Liquids and Deep Eutectic Solvents
journal, May 2014

  • Hartley, Jennifer M.; Ip, Chung-Man; Forrest, Gregory C. H.
  • Inorganic Chemistry, Vol. 53, Issue 12
  • DOI: 10.1021/ic500824r

The effect of additives on zinc electrodeposition from deep eutectic solvents
journal, May 2011


Electrodeposition of zinc–tin alloys from deep eutectic solvents based on choline chloride
journal, January 2007

  • Abbott, Andrew P.; Capper, Glen; McKenzie, Katy J.
  • Journal of Electroanalytical Chemistry, Vol. 599, Issue 2, p. 288-294
  • DOI: 10.1016/j.jelechem.2006.04.024

The Stokes-Einstein Law for Diffusion in Solution
journal, December 1924

  • Miller, C. C.
  • Proceedings of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 106, Issue 740
  • DOI: 10.1098/rspa.1924.0100

The chemistry of the additives in an acid copper electroplating bath
journal, October 1992

  • Healy, John P.; Pletcher, Derek; Goodenough, Mark
  • Journal of Electroanalytical Chemistry, Vol. 338, Issue 1-2
  • DOI: 10.1016/0022-0728(92)80420-9

Chronocoulometric studies of chloride adsorption at the Pt(111) electrode surface
journal, September 2000


Determination of the Gibbs excess of H adsorbed at a Pt(111) electrode surface in the presence of co-adsorbed chloride
journal, August 2005

  • Garcia-Araez, Nuria; Climent, Victor; Herrero, Enrique
  • Journal of Electroanalytical Chemistry, Vol. 582, Issue 1-2
  • DOI: 10.1016/j.jelechem.2005.01.031

Theory and experiment on the cuprous–cupric electron transfer rate at a copper electrode
journal, April 1999

  • Halley, J. W.; Smith, B. B.; Walbran, S.
  • The Journal of Chemical Physics, Vol. 110, Issue 13
  • DOI: 10.1063/1.478557

Copper(II) complexes with chloride ion
journal, July 1986


Chloride complexes of copper(I) chloride in aqueous solution
journal, September 1980


Ionic liquids form ideal solutions
journal, January 2011

  • Abbott, Andrew P.; Frisch, Gero; Garrett, Holly
  • Chemical Communications, Vol. 47, Issue 43
  • DOI: 10.1039/c1cc14801j