Understanding the Role of Complexation in the Charge-Transfer Kinetics of the Cu2+ + e ↔ Cu1+ Redox Reaction in Ethaline Deep Eutectic Solvent

Shen, Dai; Vukmirovic, Miomir B.; Akolkar, Rohan

doi:10.1149/2.1211915jes

Title: Understanding the Role of Complexation in the Charge-Transfer Kinetics of the Cu²⁺ + e ↔ Cu¹⁺ Redox Reaction in Ethaline Deep Eutectic Solvent

Journal Article · 14 November 2019 · Journal of the Electrochemical Society

DOI: https://doi.org/10.1149/2.1211915jes · OSTI ID:1574915

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Case Western Reserve Univ., Cleveland, OH (United States). Dept. of Chemical and Biomolecular Engineering
Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Div.

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 α_c, 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.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Breakthrough Electrolytes for Energy Storage (BEES); Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0012704

OSTI ID:: 1574915

Report Number(s):: BNL--212339-2019-JAAM

Journal Information:: Journal of the Electrochemical Society, Journal Name: Journal of the Electrochemical Society Journal Issue: 15 Vol. 166; ISSN 0013-4651

Publisher:: The Electrochemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Complexation
Deep eutectic solvent
Electrochemical Engineering
Electrochemical redox reactions
Electrodeposition - Copper

Title: Understanding the Role of Complexation in the Charge-Transfer Kinetics of the Cu2+ + e ↔ Cu1+ Redox Reaction in Ethaline Deep Eutectic Solvent

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Title: Understanding the Role of Complexation in the Charge-Transfer Kinetics of the Cu²⁺ + e ↔ Cu¹⁺ Redox Reaction in Ethaline Deep Eutectic Solvent