Electrochemistry of the NaI-AlBr 3 Molten Salt System: A Redox-Active, Low-Temperature Molten Salt Electrolyte
Abstract
NaI-AlBr 3 is a very appealing low melting temperature (<100 °C), salt system for use as an electrochemically-active electrolyte. This system was investigated for its electrochemical and physical properties with focus to energy storage considerations. A simple phase diagram was generated; at >100 °C, lower NaI concentrations had two partially miscible liquid phases, while higher NaI concentrations had solid particles. Considering the fully molten regime, electrical conductivities were evaluated over 5–25 mol% NaI and 110 °C–140 °C. Conductivities of 6.8–38.9 mS cm −1 were observed, increasing with temperature and NaI concentration. Effective diffusion coefficients of the I − /I 3 − redox species were found to decrease with both increasing NaI concentration and increasing applied potential. Regardless, oxidation current density at 3.6 V vs Na/Na + was observed to increase with increasing NaI concentration over 5–25 mol%. Finally, the critical interface between the molten salt electrolyte and electrode materials was found to significantly affect reaction kinetics. When carbon was used instead of tungsten, an adsorbed species, most likely I 2 , blocked surface sites and significantly decreased current densities at high potentials. This study shows the NaI-AlBr 3 system offers an attractive, low-temperature molten salt electrolyte that could be usefulmore »
- Authors:
- Publication Date:
- Research Org.:
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
- Sponsoring Org.:
- USDOE Office of Electricity (OE), Advanced Grid Research & Development. Power Systems Engineering Research; USDOE National Nuclear Security Administration (NNSA)
- OSTI Identifier:
- 1835446
- Alternate Identifier(s):
- OSTI ID: 1772937
- Report Number(s):
- SAND-2021-3076J
Journal ID: ISSN 0013-4651
- Grant/Contract Number:
- AC04-94AL85000; NA0003525
- Resource Type:
- Published Article
- Journal Name:
- Journal of the Electrochemical Society
- Additional Journal Information:
- Journal Name: Journal of the Electrochemical Society Journal Volume: 168 Journal Issue: 3; Journal ID: ISSN 0013-4651
- Publisher:
- The Electrochemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Percival, Stephen J., Lee, Rose Y., Gross, Martha M., Peretti, Amanda S., Small, Leo J., and Spoerke, Erik D. Electrochemistry of the NaI-AlBr 3 Molten Salt System: A Redox-Active, Low-Temperature Molten Salt Electrolyte. United States: N. p., 2021.
Web. doi:10.1149/1945-7111/abebae.
Percival, Stephen J., Lee, Rose Y., Gross, Martha M., Peretti, Amanda S., Small, Leo J., & Spoerke, Erik D. Electrochemistry of the NaI-AlBr 3 Molten Salt System: A Redox-Active, Low-Temperature Molten Salt Electrolyte. United States. https://doi.org/10.1149/1945-7111/abebae
Percival, Stephen J., Lee, Rose Y., Gross, Martha M., Peretti, Amanda S., Small, Leo J., and Spoerke, Erik D. Thu .
"Electrochemistry of the NaI-AlBr 3 Molten Salt System: A Redox-Active, Low-Temperature Molten Salt Electrolyte". United States. https://doi.org/10.1149/1945-7111/abebae.
@article{osti_1835446,
title = {Electrochemistry of the NaI-AlBr 3 Molten Salt System: A Redox-Active, Low-Temperature Molten Salt Electrolyte},
author = {Percival, Stephen J. and Lee, Rose Y. and Gross, Martha M. and Peretti, Amanda S. and Small, Leo J. and Spoerke, Erik D.},
abstractNote = {NaI-AlBr 3 is a very appealing low melting temperature (<100 °C), salt system for use as an electrochemically-active electrolyte. This system was investigated for its electrochemical and physical properties with focus to energy storage considerations. A simple phase diagram was generated; at >100 °C, lower NaI concentrations had two partially miscible liquid phases, while higher NaI concentrations had solid particles. Considering the fully molten regime, electrical conductivities were evaluated over 5–25 mol% NaI and 110 °C–140 °C. Conductivities of 6.8–38.9 mS cm −1 were observed, increasing with temperature and NaI concentration. Effective diffusion coefficients of the I − /I 3 − redox species were found to decrease with both increasing NaI concentration and increasing applied potential. Regardless, oxidation current density at 3.6 V vs Na/Na + was observed to increase with increasing NaI concentration over 5–25 mol%. Finally, the critical interface between the molten salt electrolyte and electrode materials was found to significantly affect reaction kinetics. When carbon was used instead of tungsten, an adsorbed species, most likely I 2 , blocked surface sites and significantly decreased current densities at high potentials. This study shows the NaI-AlBr 3 system offers an attractive, low-temperature molten salt electrolyte that could be useful to many applied systems, though composition and electrode material must be considered.},
doi = {10.1149/1945-7111/abebae},
journal = {Journal of the Electrochemical Society},
number = 3,
volume = 168,
place = {United States},
year = {Thu Mar 11 00:00:00 EST 2021},
month = {Thu Mar 11 00:00:00 EST 2021}
}
https://doi.org/10.1149/1945-7111/abebae
Works referenced in this record:
Phase diagram of the sodium chloride-aluminum chloride system near equimolar composition, with determination of the cryoscopic constant, the enthalpy of melting, and oxide contaminations
journal, February 1984
- Berg, Rolf W.; Hjuler, Hans Aage; Bjerrum, Niels J.
- Inorganic Chemistry, Vol. 23, Issue 5
Ionic-Liquid-Mediated Extraction and Separation Processes for Bioactive Compounds: Past, Present, and Future Trends
journal, February 2017
- Ventura, Sónia P. M.; e. Silva, Francisca A.; Quental, Maria V.
- Chemical Reviews, Vol. 117, Issue 10
Electrodeposition of aluminium from nonaqueous organic electrolytic systems and room temperature molten salts
journal, January 1997
- Zhao, Yuguang; VanderNoot, T. J.
- Electrochimica Acta, Vol. 42, Issue 1
First- and second-order chemical-electrochemical mechanisms
journal, August 1986
- Savéant, J. M.; Xu, F.
- Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 208, Issue 2
On the incorporation of protic ionic liquids imbibed in large pore zeolites to polybenzimidazole membranes for high temperature proton exchange membrane fuel cells
journal, January 2013
- Eguizábal, A.; Lemus, J.; Pina, M. P.
- Journal of Power Sources, Vol. 222
The Conductivity of Imidazolium-Based Ionic Liquids from (248 to 468) K. B. Variation of the Anion †
journal, May 2010
- Zech, Oliver; Stoppa, Alexander; Buchner, Richard
- Journal of Chemical & Engineering Data, Vol. 55, Issue 5
Conductivity of ionic liquids in mixtures
journal, January 2006
- Jarosik, Anna; Krajewski, Sebastian R.; Lewandowski, Andrzej
- Journal of Molecular Liquids, Vol. 123, Issue 1
Electrochemical Production of Si without Generation of CO 2 Based on the Use of a Dimensionally Stable Anode in Molten CaCl 2
journal, September 2019
- Ge, Jianbang; Zou, Xingli; Almassi, Soroush
- Angewandte Chemie International Edition, Vol. 58, Issue 45
Electrochemistry of the NaI-AlCl 3 Molten Salt System for Use as Catholyte in Sodium Metal Batteries
journal, January 2018
- Percival, Stephen J.; Small, Leo J.; Spoerke, Erik D.
- Journal of The Electrochemical Society, Vol. 165, Issue 14
An Electrochemical Quartz Crystal Microbalance Study on Electrodeposition of Aluminum and Aluminum-Manganese Alloys
journal, January 2017
- Ispas, A.; Wolff, E.; Bund, A.
- Journal of The Electrochemical Society, Vol. 164, Issue 8
LiCl-LiI molten salt electrolyte with bismuth-lead positive electrode for liquid metal battery
journal, February 2018
- Kim, Junsoo; Shin, Donghyeok; Jung, Youngjae
- Journal of Power Sources, Vol. 377
Electrochemical growth of a corrosion-resistant multi-layer scale to enable an oxygen-evolution inert anode in molten carbonate
journal, July 2018
- Tang, Diyong; Zheng, Kaiyuan; Yin, Huayi
- Electrochimica Acta, Vol. 279
Ultra-Sensitive Potentiometric Measurements of Dilute Redox Molecule Solutions and Determination of Sensitivity Factors at Platinum Ultramicroelectrodes
journal, August 2017
- Percival, Stephen J.; Bard, Allen J.
- Analytical Chemistry, Vol. 89, Issue 18
Viscosity of Aluminium Chloride and Acidic Sodium Chloroaluminate Melts
journal, January 1979
- Brockner, W.; Tørklep, K.; Øye, H. A.
- Berichte der Bunsengesellschaft für physikalische Chemie, Vol. 83, Issue 1
Electrochemical Energy Storage for Green Grid
journal, May 2011
- Yang, Zhenguo; Zhang, Jianlu; Kintner-Meyer, Michael C. W.
- Chemical Reviews, Vol. 111, Issue 5, p. 3577-3613
Ionic Liquid Redox Catholyte for High Energy Efficiency, Low-Cost Energy Storage
journal, April 2015
- Xue, Leigang; Tucker, Telpriore G.; Angell, C. Austen
- Advanced Energy Materials, Vol. 5, Issue 12
Liquid-metal electrode to enable ultra-low temperature sodium–beta alumina batteries for renewable energy storage
journal, August 2014
- Lu, Xiaochuan; Li, Guosheng; Kim, Jin Y.
- Nature Communications, Vol. 5, Issue 1
Ionic Liquids at Electrified Interfaces
journal, March 2014
- Fedorov, Maxim V.; Kornyshev, Alexei A.
- Chemical Reviews, Vol. 114, Issue 5
Liquid-Tin-Assisted Molten Salt Electrodeposition of Photoresponsive n-Type Silicon Films
journal, November 2017
- Peng, Junjun; Yin, Huayi; Zhao, Ji
- Advanced Functional Materials, Vol. 28, Issue 1
Challenges and obstacles in the development of sodium–air batteries
journal, December 2013
- Peled, Emanuel; Golodnitsky, Diana; Hadar, Roni
- Journal of Power Sources, Vol. 244
Review—Electrochemical Surface Finishing and Energy Storage Technology with Room-Temperature Haloaluminate Ionic Liquids and Mixtures
journal, January 2017
- Tsuda, Tetsuya; Stafford, Gery R.; Hussey, Charles L.
- Journal of The Electrochemical Society, Vol. 164, Issue 8
Low-Temperature Molten Salt Electrolytes for Membrane-Free Sodium Metal Batteries
journal, January 2015
- Spatocco, Brian L.; Ouchi, Takanari; Lambotte, Guillaume
- Journal of The Electrochemical Society, Vol. 162, Issue 14
Critical temperature and coexistence curve for aluminum bromide
journal, May 1968
- Johnson, J. W.; Silva, W. J.; Cubicciotti, Daniel
- The Journal of Physical Chemistry, Vol. 72, Issue 5
Molten iodide salt electrolyte for low-temperature low-cost sodium-based liquid metal battery
journal, November 2020
- Gong, Qing; Ding, Wenjin; Bonk, Alexander
- Journal of Power Sources, Vol. 475
Challenges and perspectives on high and intermediate-temperature sodium batteries
journal, June 2017
- Hueso, Karina B.; Palomares, Verónica; Armand, Michel
- Nano Research, Vol. 10, Issue 12
The Interaction of Aluminum Bromide and Sodium Iodide
journal, August 1950
- Daniel, J. L.; Gregory, N. W.
- Journal of the American Chemical Society, Vol. 72, Issue 8
Electrochemical Reactivity in Room-Temperature Ionic Liquids
journal, July 2008
- Hapiot, Philippe; Lagrost, Corinne
- Chemical Reviews, Vol. 108, Issue 7
High-Efficiency and Stable Mesoscopic Dye-Sensitized Solar Cells Based on a High Molar Extinction Coefficient Ruthenium Sensitizer and Nonvolatile Electrolyte
journal, April 2007
- Kuang, D.; Klein, C.; Ito, S.
- Advanced Materials, Vol. 19, Issue 8, p. 1133-1137
Electrochemical Synthesis of Nanomaterials in Molten Salts: I. Synthesis of Tantalum Monoxide Nanoneedles
journal, January 2017
- Kuznetsov, S. A.
- Journal of The Electrochemical Society, Vol. 164, Issue 8
Sodium-Metal Halide and Sodium-Air Batteries
journal, June 2014
- Ha , Seongmin; Kim , Jae-Kwang; Choi, Aram
- ChemPhysChem, Vol. 15, Issue 10
The system NaCl-AlCl3
journal, July 1974
- Levin, Ernest M.; Kinney, J. F.; Wells, R. D.
- Journal of Research of the National Bureau of Standards Section A: Physics and Chemistry, Vol. 78A, Issue 4
Electrochemical synthesis, morphological and structural characteristics of carbon nanomaterials produced in molten salts
journal, September 2016
- Novoselova, Inessa A.; Kuleshov, Sergei V.; Volkov, Sergei V.
- Electrochimica Acta, Vol. 211
A New Ionic Liquid Electrolyte Enhances the Conversion Efficiency of Dye-Sensitized Solar Cells
journal, December 2003
- Wang, Peng; Zakeeruddin, Shaik M.; Moser, Jacques-E.
- The Journal of Physical Chemistry B, Vol. 107, Issue 48
Separation behavior of nickel and cobalt in a LiCl-KCl-NiCl2 molten salt by electrorefining process
journal, June 2020
- Choi, Woo-Seok; Cho, Soo-Haeng; Lee, Young-Jun
- Journal of Electroanalytical Chemistry, Vol. 866
Next generation molten NaI batteries for grid scale energy storage
journal, August 2017
- Small, Leo J.; Eccleston, Alexis; Lamb, Joshua
- Journal of Power Sources, Vol. 360
Toward Cost-Effective Manufacturing of Silicon Solar Cells: Electrodeposition of High-Quality Si Films in a CaCl 2 -based Molten Salt
journal, October 2017
- Yang, Xiao; Ji, Li; Zou, Xingli
- Angewandte Chemie International Edition, Vol. 56, Issue 47
A Practical Beginner’s Guide to Cyclic Voltammetry
journal, November 2017
- Elgrishi, Noémie; Rountree, Kelley J.; McCarthy, Brian D.
- Journal of Chemical Education, Vol. 95, Issue 2
Electrochemical Separation of Lanthanum Oxide in Molten FLiNaK Salt
journal, July 2020
- Yang, Qiufeng; Ge, Jianbang; Wang, Yafei
- Nuclear Technology, Vol. 206, Issue 11
Electrochemical Formation of a p–n Junction on Thin Film Silicon Deposited in Molten Salt
journal, November 2017
- Zou, Xingli; Ji, Li; Yang, Xiao
- Journal of the American Chemical Society, Vol. 139, Issue 45
Ionic liquid doped polybenzimidazole membranes for high temperature Proton Exchange Membrane fuel cell applications
journal, January 2013
- van de Ven, Erik; Chairuna, Anisa; Merle, Géraldine
- Journal of Power Sources, Vol. 222
Tetraalkylammonium trifluoromethanesulfonates as supporting electrolytes
journal, December 1972
- Rousseau, K.; Farrington, G. C.; Dolphin, D.
- The Journal of Organic Chemistry, Vol. 37, Issue 24
Direct determination of diffusion coefficients by chronoamperometry at microdisk electrodes
journal, June 1991
- Denuault, Guy; Mirkin, Michael V.; Bard, Alien J.
- Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 308, Issue 1-2
Low-Temperature Molten Sodium Batteries
journal, November 2020
- Gross, Martha M.; Percival, Stephen J.; Small, Leo J.
- ACS Applied Energy Materials, Vol. 3, Issue 11
Study of the Formation and Quick Growth of Thick Oxide Films Using Platinum Nanoelectrodes as a Model Electrocatalyst
journal, September 2014
- Percival, Stephen J.; Zhang, Bo
- Langmuir, Vol. 30, Issue 37