Practical thermodynamic quantities for aqueous vanadium- and iron-based flow batteries

Hudak, Nicholas S.

doi:10.1016/j.jpowsour.2013.12.089

Practical thermodynamic quantities for aqueous vanadium- and iron-based flow batteries

Journal Article · Tue Dec 31 00:00:00 EST 2013 · Journal of Power Sources

DOI:https://doi.org/10.1016/j.jpowsour.2013.12.089· OSTI ID:1113052

Hudak, Nicholas S. ^[1]

Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

A simple method for experimentally determining thermodynamic quantities for flow battery cell reactions is presented. Equilibrium cell potentials, temperature derivatives of cell potential (dE/dT), Gibbs free energies, and entropies are reported here for all-vanadium, iron–vanadium, and iron–chromium flow cells with state-of-the-art solution compositions. Proof is given that formal potentials and formal temperature coefficients can be used with modified forms of the Nernst Equation to quantify the thermodynamics of flow cell reactions as a function of state-of-charge. Such empirical quantities can be used in thermo-electrochemical models of flow batteries at the cell or system level. In most cases, the thermodynamic quantities measured here are significantly different from standard values reported and used previously in the literature. The data reported here are also useful in the selection of operating temperatures for flow battery systems. Because higher temperatures correspond to lower equilibrium cell potentials for the battery chemistries studied here, it can be beneficial to charge a cell at higher temperature and discharge at lower temperature. As a result, proof-of-concept of improved voltage efficiency with the use of such non-isothermal cycling is given for the all-vanadium redox flow battery, and the effect is shown to be more pronounced at lower current densities.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC04-94AL85000

OSTI ID:: 1113052

Report Number(s):: SAND--2013-8072J; PII: S0378775313020685

Journal Information:: Journal of Power Sources, Journal Name: Journal of Power Sources Journal Issue: C Vol. 269; ISSN 0378-7753

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (40)

Recent Progress in Redox Flow Battery Research and Development Wang, Wei; Luo, Qingtao; Li, Bin Advanced Functional Materials, Vol. 23, Issue 8, p. 970-986 https://doi.org/10.1002/adfm.201200694	journal	September 2012
A Stable Vanadium Redox-Flow Battery with High Energy Density for Large-Scale Energy Storage Li, Liyu; Kim, Soowhan; Wang, Wei Advanced Energy Materials, Vol. 1, Issue 3, p. 394-400 https://doi.org/10.1002/aenm.201100008	journal	March 2011
A New Fe/V Redox Flow Battery Using a Sulfuric/Chloric Mixed-Acid Supporting Electrolyte Wang, Wei; Nie, Zimin; Chen, Baowei Advanced Energy Materials, Vol. 2, Issue 4 https://doi.org/10.1002/aenm.201100527	journal	February 2012
Thermodynamics of Vanadium Redox Flow Batteries - Electrochemical and Calorimetric Investigations Heintz, A.; Illenberger, Ch. Berichte der Bunsengesellschaft für physikalische Chemie, Vol. 102, Issue 10 https://doi.org/10.1002/bbpc.199800009	journal	October 1998
The importance of key operational variables and electrolyte monitoring to the performance of an all vanadium redox flow battery: Performance of an all vanadium redox flow battery Watt-Smith, M. J.; Ridley, P.; Wills, R. G. A. Journal of Chemical Technology & Biotechnology, Vol. 88, Issue 1 https://doi.org/10.1002/jctb.3870	journal	August 2012
Thermodynamic diagrams for the vanadium-water system at 298·15K Post, K.; Robins, R. G. Electrochimica Acta, Vol. 21, Issue 6 https://doi.org/10.1016/0013-4686(76)85115-8	journal	June 1976
The thermodynamic and thermoelectric properties of LixTiS2 and LixCoO2 Honders, A.; Derkinderen, J.; Vanheeren, A. Solid State Ionics, Vol. 14, Issue 3 https://doi.org/10.1016/0167-2738(84)90100-0	journal	November 1984
Optimization studies on a Fe/Cr redox flow battery Lopez-Atalaya, M.; Codina, G.; Perez, J. R. Journal of Power Sources, Vol. 39, Issue 2, p. 147-154 https://doi.org/10.1016/0378-7753(92)80133-v	journal	January 1992
Cycling performance and efficiency of sulfonated poly(sulfone) membranes in vanadium redox flow batteries Kim, Soowhan; Yan, Jingling; Schwenzer, Birgit Electrochemistry Communications, Vol. 12, Issue 11 https://doi.org/10.1016/j.elecom.2010.09.018	journal	November 2010
Open circuit voltage of vanadium redox flow batteries: Discrepancy between models and experiments Knehr, K. W.; Kumbur, E. C. Electrochemistry Communications, Vol. 13, Issue 4 https://doi.org/10.1016/j.elecom.2011.01.020	journal	April 2011
A dynamic performance model for redox-flow batteries involving soluble species Shah, A. A.; Watt-Smith, M. J.; Walsh, F. C. Electrochimica Acta, Vol. 53, Issue 27, p. 8087-8100 https://doi.org/10.1016/j.electacta.2008.05.067	journal	November 2008
A simple model for the vanadium redox battery You, Dongjiang; Zhang, Huamin; Chen, Jian Electrochimica Acta, Vol. 54, Issue 27 https://doi.org/10.1016/j.electacta.2009.06.086	journal	November 2009
Non-isothermal modelling of the all-vanadium redox flow battery Al-Fetlawi, H.; Shah, A. A.; Walsh, F. C. Electrochimica Acta, Vol. 55, Issue 1 https://doi.org/10.1016/j.electacta.2009.08.009	journal	December 2009
Dynamic modelling of hydrogen evolution effects in the all-vanadium redox flow battery Shah, A. A.; Al-Fetlawi, H.; Walsh, F. C. Electrochimica Acta, Vol. 55, Issue 3 https://doi.org/10.1016/j.electacta.2009.10.022	journal	January 2010
Modelling the effects of oxygen evolution in the all-vanadium redox flow battery Al-Fetlawi, H.; Shah, A. A.; Walsh, F. C. Electrochimica Acta, Vol. 55, Issue 9 https://doi.org/10.1016/j.electacta.2009.12.085	journal	March 2010
3-D pore-scale resolved model for coupled species/charge/fluid transport in a vanadium redox flow battery Qiu, Gang; Joshi, Abhijit S.; Dennison, C. R. Electrochimica Acta, Vol. 64 https://doi.org/10.1016/j.electacta.2011.12.065	journal	March 2012
Analysis of a model for the operation of a vanadium redox battery Vynnycky, M. Energy, Vol. 36, Issue 4 https://doi.org/10.1016/j.energy.2010.03.060	journal	April 2011
Redox flow cells for energy conversion Ponce de Leon, C.; Frias-Ferrer, A.; Gonzalez-Garcia, J. Journal of Power Sources, Vol. 160, Issue 1, p. 716-732 https://doi.org/10.1016/j.jpowsour.2006.02.095	journal	September 2006
Fe/V redox flow battery electrolyte investigation and optimization Li, Bin; Li, Liyu; Wang, Wei Journal of Power Sources, Vol. 229 https://doi.org/10.1016/j.jpowsour.2012.11.119	journal	May 2013
The effects of surface modification on carbon felt electrodes for use in vanadium redox flow batteries Kim, Ki Jae; Kim, Young-Jun; Kim, Jae-Hun Materials Chemistry and Physics, Vol. 131, Issue 1-2 https://doi.org/10.1016/j.matchemphys.2011.10.022	journal	December 2011
Water transfer behaviour across cation exchange membranes in the vanadium redox battery Sukkar, Theresa; Skyllas-Kazacos, Maria Journal of Membrane Science, Vol. 222, Issue 1-2 https://doi.org/10.1016/s0376-7388(03)00309-0	journal	September 2003
Electrochemical Energy Storage for Green Grid Yang, Zhenguo; Zhang, Jianlu; Kintner-Meyer, Michael C. W. Chemical Reviews, Vol. 111, Issue 5, p. 3577-3613 https://doi.org/10.1021/cr100290v	journal	May 2011
Thermochemistry and oxidation potentials of vanadium, niobium, and tantalum Hepler, Loren G.; Hill, John Oxford; Worsley, Ian G. Chemical Reviews, Vol. 71, Issue 1 https://doi.org/10.1021/cr60269a006	journal	February 1971
The Entropy and Structure of the Pervanadyl Ion LaSalle, M. J.; Cobble, James W. The Journal of Physical Chemistry, Vol. 59, Issue 6 https://doi.org/10.1021/j150528a010	journal	June 1955
Electrochemical Studies on Vanadium Salts. III. The Vanadic-Vanadous Oxidation-Reduction Potential ¹ Jones, Grinnell; Colvin, John Henry Journal of the American Chemical Society, Vol. 66, Issue 9 https://doi.org/10.1021/ja01237a047	journal	September 1944
The Constitution of the Pentavalent Vanadium Ion in Acid Solution Carpenter, Joseph E. Journal of the American Chemical Society, Vol. 56, Issue 9 https://doi.org/10.1021/ja01324a008	journal	September 1934
The Reduction Potential of Vanadic Acid to Vanadyl Ion in Hydrochloric Acid Solutions Coryell, Charles D.; Yost, Don M. Journal of the American Chemical Society, Vol. 55, Issue 5 https://doi.org/10.1021/ja01332a018	journal	May 1933
Standard electrode potential of Fe3+ + e- = Fe2+ from 5-35.deg. Whittemore, Donald O.; Langmuir, Donald Journal of Chemical & Engineering Data, Vol. 17, Issue 3 https://doi.org/10.1021/je60054a002	journal	July 1972
A new redox flow battery using Fe/V redox couples in chloride supporting electrolyte Wang, Wei; Kim, Soowhan; Chen, Baowei Energy & Environmental Science, Vol. 4, Issue 10, p. 4068-4073 https://doi.org/10.1039/c0ee00765j	journal	January 2011
Standard Electrode Potentials and Temperature Coefficients in Water at 298.15 K Bratsch, Steven G. Journal of Physical and Chemical Reference Data, Vol. 18, Issue 1 https://doi.org/10.1063/1.555839	journal	January 1989
Electrical Energy Storage for the Grid: A Battery of Choices Dunn, B.; Kamath, H.; Tarascon, J. -M. Science, Vol. 334, Issue 6058 https://doi.org/10.1126/science.1212741	journal	November 2011
Entropy measurements on Li _x TiS ₂ Dahn, J. R.; Haering, R. R. Canadian Journal of Physics, Vol. 61, Issue 7 https://doi.org/10.1139/p83-140	journal	July 1983
Thermal-Electrochemical Modeling of Battery Systems Gu, W. B.; Wang, C. Y. Journal of The Electrochemical Society, Vol. 147, Issue 8 https://doi.org/10.1149/1.1393625	journal	January 2000
A General Energy Balance for Battery Systems Bernardi, D. Journal of The Electrochemical Society, Vol. 132, Issue 1 https://doi.org/10.1149/1.2113792	journal	January 1985
A Mathematical Model for the Iron/Chromium Redox Battery Fedkiw, Peter S. Journal of The Electrochemical Society, Vol. 131, Issue 4 https://doi.org/10.1149/1.2115676	journal	January 1984
The Temperature Coefficients of Electrode Potentials deBethune, A. J.; Licht, T. S.; Swendeman, N. Journal of The Electrochemical Society, Vol. 106, Issue 7, p. 616-625 https://doi.org/10.1149/1.2427448	journal	January 1959
Progress in Flow Battery Research and Development Skyllas-Kazacos, M.; Chakrabarti, M. H.; Hajimolana, S. A. Journal of The Electrochemical Society, Vol. 158, Issue 8, p. R55-R79 https://doi.org/10.1149/1.3599565	journal	June 2011
Electrochemical Model of the Fe/V Redox Flow Battery Stephenson, David; Kim, Soowhan; Chen, Feng Journal of The Electrochemical Society, Vol. 159, Issue 12 https://doi.org/10.1149/2.052212jes	journal	January 2012
Optimization studies on a Fe/Cr redox flow battery Lopez-Atalaya, M.; Codina, G.; Perez, J. R. Journal of Power Sources, Vol. 39, Issue 2, p. 147-154 https://doi.org/10.1016/0378-7753(92)80133-V	journal	January 1992
Water transfer behaviour across cation exchange membranes in the vanadium redox battery Sukkar, Theresa; Skyllas-Kazacos, Maria Journal of Membrane Science, Vol. 222, Issue 1-2 https://doi.org/10.1016/S0376-7388(03)00309-0	journal	September 2003

Cited By (1)

A One-Dimensional Stack Model for Redox Flow Battery Analysis and Operation Barton, John L.; Brushett, Fikile R. Batteries, Vol. 5, Issue 1 https://doi.org/10.3390/batteries5010025	journal	February 2019

Similar Records

Asymmetric vanadium-based aqueous flow batteries

Book · Sun Jan 08 23:00:00 EST 2023 · OSTI ID:2229127

An experimental database of cell performance for vanadium redox flow battery

Dataset · Mon Jan 11 23:00:00 EST 2021 · OSTI ID:1862881

A STUDY OF THE THERMODYNAMIC PROPERTIES OF THE VANADIUM-IRON ALLOY SYSTEM

Technical Report · Thu Jan 31 23:00:00 EST 1963 · OSTI ID:4696193

Related Subjects

25 ENERGY STORAGE
Nernst equation
entropy
flow battery
formal potential
non-isothermal
thermodynamics

Practical thermodynamic quantities for aqueous vanadium- and iron-based flow batteries

Citation Formats

References (40)

Cited By (1)

Similar Records

Related Subjects