Long-Term Stability of Ferri-/Ferrocyanide as an Electroactive Component for Redox Flow Battery Applications: On the Origin of Apparent Capacity Fade

Fell, Eric M.; De Porcellinis, Diana; Jing, Yan; Gutierrez-Venegas, Valeria; George, Thomas Y.; Gordon, Roy G.; Granados-Focil, Sergio; Aziz, Michael J.

doi:10.1149/1945-7111/ace936

Title: Long-Term Stability of Ferri-/Ferrocyanide as an Electroactive Component for Redox Flow Battery Applications: On the Origin of Apparent Capacity Fade

Journal Article · Fri Jul 28 00:00:00 EDT 2023 · Journal of the Electrochemical Society

DOI:https://doi.org/10.1149/1945-7111/ace936· OSTI ID:1992956

; De Porcellinis, Diana; Jing, Yan; Gutierrez-Venegas, Valeria;

; Gordon, Roy G.; Granados-Focil, Sergio;

Abstract We assess the suitability of potassium ferri-/ferrocyanide as an electroactive species for long-term utilization in aqueous organic redox flow batteries. A series of electrochemical and chemical characterization experiments was performed to distinguish between structural decomposition and apparent capacity fade of ferri-/ferrocyanide solutions used in the capacity-limiting side of a flow battery. Our results indicate that, in contrast with previous reports, no structural decomposition of ferri-/ferrocyanide occurs at tested pH values as high as 14 in the dark or in diffuse indoor light. Instead, an apparent capacity fade takes place due to a chemical reduction of ferricyanide to ferrocyanide, via chemical oxygen evolution reaction. We find that this parasitic process can be further exacerbated by carbon electrodes, with apparent capacity fade rates at pH 14 increasing with an increased ratio of carbon electrode surface area to ferricyanide in solution. Based on these results, we report a set of operating conditions that enables the long-duration cycling of alkaline ferri-/ferrocyanide electrolytes and demonstrate how apparent capacity fade rates can be engineered by the initial system setup. If protected from direct exposure to light, the structural stability of ferri-/ferrocyanide anions allows for their practical deployment as electroactive species in long duration energy storage applications.

View Journal Article

Cite

Export

Save

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC05-76RL01830 through PNNL subcontract 535264

OSTI ID:: 1992956

Alternate ID(s):: OSTI ID: 1991649

Journal Information:: Journal of the Electrochemical Society, Journal Name: Journal of the Electrochemical Society Vol. 170 Journal Issue: 7; ISSN 0013-4651

Publisher:: The Electrochemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (65)

Cyanide Binding to Carbonic Anhydrase. A 13C-Nuclear-Magnetic-Resonance Study Feeney, James; Burgen, Arnold S. V.; Grell, Ernst European Journal of Biochemistry, Vol. 34, Issue 1 https://doi.org/10.1111/j.1432-1033.1973.tb02735.x	journal	April 1973
Ultrastable aqueous phenazine flow batteries with high capacity operated at elevated temperatures Xu, Jiancong; Pang, Shuai; Wang, Xinyi Joule, Vol. 5, Issue 9 https://doi.org/10.1016/j.joule.2021.06.019	journal	September 2021
An aqueous, polymer-based redox-flow battery using non-corrosive, safe and low-cost materials Janoschka, Tobias; Martin, Norbert; Martin, Udo Nature, Vol. 527, Issue 7576, p. 78-81 https://doi.org/10.1038/nature15746	journal	October 2015
A Phosphonate‐Functionalized Quinone Redox Flow Battery at Near‐Neutral pH with Record Capacity Retention Rate Ji, Yunlong; Goulet, Marc‐Antoni; Pollack, Daniel A. Advanced Energy Materials, Vol. 9, Issue 12 https://doi.org/10.1002/aenm.201900039	journal	January 2019
Scalable, Green Fabrication of Single-Crystal Noble Metal Films and Nanostructures for Low-Loss Nanotechnology Applications V. Grayli, Sasan; Zhang, Xin; MacNab, Finlay C. ACS Nano, Vol. 14, Issue 6 https://doi.org/10.1021/acsnano.0c03466	journal	May 2020
Materials challenges of aqueous redox flow batteries Luo, Jian; Wang, Abigail P.; Hu, Maowei MRS Energy & Sustainability, Vol. 9, Issue 1 https://doi.org/10.1557/s43581-022-00023-1	journal	February 2022
The mechanism of decomposition of N-methyl-N-nitrosourea in aqueous solution according to¹³C and¹⁵N NMR studies: quantitative fragmentation to cyanate Bleasdale, Christine; Golding, Bernard T.; McGinnis, Joseph J. Chem. Soc., Chem. Commun., Issue 24 https://doi.org/10.1039/C39910001726	journal	January 1991
Substrate Selection for Fundamental Studies of Electrocatalysts and Photoelectrodes: Inert Potential Windows in Acidic, Neutral, and Basic Electrolyte Benck, Jesse D.; Pinaud, Blaise A.; Gorlin, Yelena PLoS ONE, Vol. 9, Issue 10 https://doi.org/10.1371/journal.pone.0107942	journal	October 2014
Two-Electron Reduction of a Vanadium(V) Nitride by CO To Release Cyanate and Open a Coordination Site Silvia, Jared S.; Cummins, Christopher C. Journal of the American Chemical Society, Vol. 131, Issue 2 https://doi.org/10.1021/ja807767w	journal	January 2009
Less can be more: Insights on the role of electrode microstructure in redox flow batteries from two-dimensional direct numerical simulations Dussi, Simone; Rycroft, Chris H. Physics of Fluids, Vol. 34, Issue 4 https://doi.org/10.1063/5.0084066	journal	April 2022
The hydrolysis and polymerization of hydrogen cyanide in alkaline solutions Marsh, J. D. F.; Martin, Margaret J. Journal of Applied Chemistry, Vol. 7, Issue 4 https://doi.org/10.1002/jctb.5010070409	journal	May 2007
Understanding the role of the porous electrode microstructure in redox flow battery performance using an experimentally validated 3D pore-scale lattice Boltzmann model Zhang, Duo; Forner-Cuenca, Antoni; Taiwo, Oluwadamilola O. Journal of Power Sources, Vol. 447 https://doi.org/10.1016/j.jpowsour.2019.227249	journal	January 2020
Investigation of Tetramorpholinohydroquinone as a Potential Catholyte in a Flow Battery Drazevic, Emil; Szabo, Csaba; Konya, Denes ACS Applied Energy Materials, Vol. 2, Issue 7 https://doi.org/10.1021/acsaem.9b00351	journal	June 2019
All iron aqueous redox flow batteries using organometallic complexes consisting of iron and 3-[bis (2-hydroxyethyl)amino]-2-hydroxypropanesulfonic acid ligand and ferrocyanide as redox couple Shin, Mingyu; Noh, Chanho; Chung, Yongjin Chemical Engineering Journal, Vol. 398 https://doi.org/10.1016/j.cej.2020.125631	journal	October 2020
Kinetics of the decomposition of potassium ferrocyanide in ultra-violet light Ašpergěr, S. Trans. Faraday Soc., Vol. 48, Issue 0 https://doi.org/10.1039/TF9524800617	journal	January 1952
Mitigating capacity fading in aqueous organic redox flow batteries through a simple electrochemical charge balancing protocol Páez, Teresa; Martínez-Cuezva, Alberto; Marcilla, Rebeca Journal of Power Sources, Vol. 512 https://doi.org/10.1016/j.jpowsour.2021.230516	journal	November 2021
CO2 absorption by aqueous NH3 solutions: speciation of ammonium carbamate, bicarbonate and carbonate by a 13C NMR study Mani, Fabrizio; Peruzzini, Maurizio; Stoppioni, Piero Green Chemistry, Vol. 8, Issue 11 https://doi.org/10.1039/b602051h	journal	January 2006
¹³C nuclear magnetic resonance and Raman investigations of aqueous carbon dioxide systems Abbott, Theresa M.; Buchanan, Gerald W.; Kruus, Peeter Canadian Journal of Chemistry, Vol. 60, Issue 8 https://doi.org/10.1139/v82-149	journal	April 1982
Symmetric-cell characterization of the redox flow battery system: Application to the detection of degradations Cazot, Mathilde; Maranzana, Gaël; Dillet, Jérôme Electrochimica Acta, Vol. 321 https://doi.org/10.1016/j.electacta.2019.134705	journal	October 2019
Method for Comparing Porous Carbon Electrode Performance in Redox Flow Batteries Wong, Andrew A.; Aziz, Michael J. Journal of The Electrochemical Society, Vol. 167, Issue 11 https://doi.org/10.1149/1945-7111/aba54d	journal	July 2020
Vermischte chemische Notizen Preuß, J. Annalen der Pharmacie, Vol. 29, Issue 3 https://doi.org/10.1002/jlac.18390290316	journal	January 1839
A Water-Miscible Quinone Flow Battery with High Volumetric Capacity and Energy Density Jin, Shijian; Jing, Yan; Kwabi, David G. ACS Energy Letters, Vol. 4, Issue 6 https://doi.org/10.1021/acsenergylett.9b00739	journal	May 2019
On Lifetime and Cost of Redox-Active Organics for Aqueous Flow Batteries Brushett, Fikile R.; Aziz, Michael J.; Rodby, Kara E. ACS Energy Letters, Vol. 5, Issue 3 https://doi.org/10.1021/acsenergylett.0c00140	journal	February 2020
Photooxidation and photoaquation of iron hexacyanide in aqueous solution: A picosecond X-ray absorption study Reinhard, M.; Penfold, T. J.; Lima, F. A. Structural Dynamics, Vol. 1, Issue 2 https://doi.org/10.1063/1.4871751	journal	March 2014
Cycling Performance and Mechanistic Insights of Ferricyanide Electrolytes in Alkaline Redox Flow Batteries Hu, Maowei; Wang, Abigail P.; Luo, Jian Advanced Energy Materials, Vol. 13, Issue 15 https://doi.org/10.1002/aenm.202203762	journal	March 2023
Flow Battery Molecular Reactant Stability Determined by Symmetric Cell Cycling Methods Goulet, Marc-Antoni; Aziz, Michael J. Journal of The Electrochemical Society, Vol. 165, Issue 7 https://doi.org/10.1149/2.0891807jes	journal	January 2018
Chelated Chromium Electrolyte Enabling High-Voltage Aqueous Flow Batteries Robb, Brian H.; Farrell, Jason M.; Marshak, Michael P. Joule, Vol. 3, Issue 10 https://doi.org/10.1016/j.joule.2019.07.002	journal	October 2019
Extremely Stable Anthraquinone Negolytes Synthesized from Common Precursors Wu, Min; Jing, Yan; Wong, Andrew A. Chem, Vol. 6, Issue 6 https://doi.org/10.1016/j.chempr.2020.03.021	journal	June 2020
Electron-transfer kinetics and mechanism of the reduction of octacyanometallates(IV) (M = Mo, W) by hydroxide ion in aqueous solution Bogdanov, Michail; Gryboś, Ryszard; Samotus, Alina Transition Metal Chemistry, Vol. 18, Issue 6 https://doi.org/10.1007/BF00191133	journal	December 1993
A π-Conjugation Extended Viologen as a Two-Electron Storage Anolyte for Total Organic Aqueous Redox Flow Batteries Luo, Jian; Hu, Bo; Debruler, Camden Angewandte Chemie International Edition, Vol. 57, Issue 1 https://doi.org/10.1002/anie.201710517	journal	December 2017
The Hydrolysis of Hydrogen Cyanide by Acids. II Krieble, Vernon K.; Peiker, Alfred L. Journal of the American Chemical Society, Vol. 55, Issue 6 https://doi.org/10.1021/ja01333a017	journal	June 1933
Isolation and Characterization of a Highly Reducing Aqueous Chromium(II) Complex Waters, Scott E.; Robb, Brian H.; Scappaticci, Steven J. Inorganic Chemistry, Vol. 61, Issue 23 https://doi.org/10.1021/acs.inorgchem.2c00699	journal	June 2022
In situ electrosynthesis of anthraquinone electrolytes in aqueous flow batteries Jing, Yan; Wu, Min; Wong, Andrew A. Green Chemistry, Vol. 22, Issue 18 https://doi.org/10.1039/D0GC02236E	journal	January 2020
THE HYDROLYSIS OF HYDROGEN CYANIDE BY ACIDS¹ Krieble, Vernon K.; McNally, James G. Journal of the American Chemical Society, Vol. 51, Issue 11 https://doi.org/10.1021/ja01386a026	journal	November 1929
A High Voltage Aqueous Zinc–Organic Hybrid Flow Battery Park, Minjoon; Beh, Eugene S.; Fell, Eric M. Advanced Energy Materials, Vol. 9, Issue 25 https://doi.org/10.1002/aenm.201900694	journal	May 2019
Application of carbon materials in redox flow batteries Chakrabarti, M. H.; Brandon, N. P.; Hajimolana, S. A. Journal of Power Sources, Vol. 253 https://doi.org/10.1016/j.jpowsour.2013.12.038	journal	May 2014
A biomimetic high-capacity phenazine-based anolyte for aqueous organic redox flow batteries Hollas, Aaron; Wei, Xiaoliang; Murugesan, Vijayakumar Nature Energy, Vol. 3, Issue 6 https://doi.org/10.1038/s41560-018-0167-3	journal	June 2018
Organic Redox Species in Aqueous Flow Batteries: Redox Potentials, Chemical Stability and Solubility Wedege, Kristina; Dražević, Emil; Konya, Denes Scientific Reports, Vol. 6, Issue 1 https://doi.org/10.1038/srep39101	journal	December 2016
Improved radical stability of viologen anolytes in aqueous organic redox flow batteries Hu, Bo; Tang, Yijie; Luo, Jian Chemical Communications, Vol. 54, Issue 50 https://doi.org/10.1039/C8CC02336K	journal	January 2018
Reversible ketone hydrogenation and dehydrogenation for aqueous organic redox flow batteries Feng, Ruozhu; Zhang, Xin; Murugesan, Vijayakumar Science, Vol. 372, Issue 6544 https://doi.org/10.1126/science.abd9795	journal	May 2021
¹³ C NMR Characterization of an Exchange Reaction between CO and CO ₂ Catalyzed by Carbon Monoxide Dehydrogenase ^† Seravalli, Javier; Ragsdale, Stephen W. Biochemistry, Vol. 47, Issue 26 https://doi.org/10.1021/bi8004522	journal	July 2008
A High Potential, Low Capacity Fade Rate Iron Complex Posolyte for Aqueous Organic Flow Batteries Gao, Jinxu; Amini, Kiana; George, Thomas Y. Advanced Energy Materials, Vol. 12, Issue 44 https://doi.org/10.1002/aenm.202202444	journal	October 2022
A Total Organic Aqueous Redox Flow Battery Employing a Low Cost and Sustainable Methyl Viologen Anolyte and 4-HO-TEMPO Catholyte Liu, Tianbiao; Wei, Xiaoliang; Nie, Zimin Advanced Energy Materials, Vol. 6, Issue 3, 1501449 https://doi.org/10.1002/aenm.201501449	journal	December 2015
Comparing Physical and Electrochemical Properties of Different Weave Patterns for Carbon Cloth Electrodes in Redox Flow Batteries Tenny, Kevin M.; Forner-Cuenca, Antoni; Chiang, Yet-Ming Journal of Electrochemical Energy Conversion and Storage, Vol. 17, Issue 4 https://doi.org/10.1115/1.4046661	journal	April 2020
Revisiting the cycling stability of ferrocyanide in alkaline media for redox flow batteries Páez, Teresa; Martínez-Cuezva, Alberto; Palma, Jesús Journal of Power Sources, Vol. 471 https://doi.org/10.1016/j.jpowsour.2020.228453	journal	September 2020
Elucidating the Nuanced Effects of Thermal Pretreatment on Carbon Paper Electrodes for Vanadium Redox Flow Batteries Greco, Katharine V.; Forner-Cuenca, Antoni; Mularczyk, Adrian ACS Applied Materials & Interfaces, Vol. 10, Issue 51 https://doi.org/10.1021/acsami.8b15793	journal	October 2018
Toward a Low-Cost Alkaline Zinc-Iron Flow Battery with a Polybenzimidazole Custom Membrane for Stationary Energy Storage Yuan, Zhizhang; Duan, Yinqi; Liu, Tao iScience, Vol. 3 https://doi.org/10.1016/j.isci.2018.04.006	journal	May 2018
Symmetry-breaking design of an organic iron complex catholyte for a long cyclability aqueous organic redox flow battery Li, Xiang; Gao, Peiyuan; Lai, Yun-Yu Nature Energy, Vol. 6, Issue 9 https://doi.org/10.1038/s41560-021-00879-6	journal	August 2021
In situ electrochemical recomposition of decomposed redox-active species in aqueous organic flow batteries Jing, Yan; Zhao, Evan Wenbo; Goulet, Marc-Antoni Nature Chemistry https://doi.org/10.1038/s41557-022-00967-4	journal	June 2022
A Comparative Study of Compressive Effects on the Morphology and Performance of Carbon Paper and Cloth Electrodes in Redox Flow Batteries Tenny, Kevin M.; Greco, Katharine V.; van der Heijden, Maxime Energy Technology, Vol. 10, Issue 8 https://doi.org/10.1002/ente.202101162	journal	June 2022
Unraveling pH dependent cycling stability of ferricyanide/ferrocyanide in redox flow batteries Luo, Jian; Sam, Alyssa; Hu, Bo Nano Energy, Vol. 42 https://doi.org/10.1016/j.nanoen.2017.10.057	journal	December 2017
An Aqueous Redox-Flow Battery with High Capacity and Power: The TEMPTMA/MV System Janoschka, Tobias; Martin, Norbert; Hager, Martin D. Angewandte Chemie International Edition, Vol. 55, Issue 46 https://doi.org/10.1002/anie.201606472	journal	October 2016
Alkaline quinone flow battery Lin, K.; Chen, Q.; Gerhardt, M. R. Science, Vol. 349, Issue 6255, p. 1529-1532 https://doi.org/10.1126/science.aab3033	journal	September 2015
A Sustainable Redox Flow Battery with Alizarin-Based Aqueous Organic Electrolyte Liu, Yiyang; Lu, Shanfu; Chen, Sian ACS Applied Energy Materials, Vol. 2, Issue 4 https://doi.org/10.1021/acsaem.8b01512	journal	February 2019
Effects of pH on the degradation of aqueous ferricyanide by photolysis and photocatalysis under solar radiation Arellano, Carlos Antonio Pineda; Martínez, Susana Silva Solar Energy Materials and Solar Cells, Vol. 94, Issue 2 https://doi.org/10.1016/j.solmat.2009.10.008	journal	February 2010
A Neutral pH Aqueous Organic–Organometallic Redox Flow Battery with Extremely High Capacity Retention Beh, Eugene S.; De Porcellinis, Diana; Gracia, Rebecca L. ACS Energy Letters, Vol. 2, Issue 3 https://doi.org/10.1021/acsenergylett.7b00019	journal	February 2017
Cyano Compounds, Inorganic Gail, Ernst; Gos, Stephen; Kulzer, Rupprecht Ullmann's Encyclopedia of Industrial Chemistry https://doi.org/10.1002/14356007.a08_159.pub3	book	January 2011
Exploring the Role of Electrode Microstructure on the Performance of Non-Aqueous Redox Flow Batteries Forner-Cuenca, Antoni; Penn, Emily E.; Oliveira, Alexandra M. Journal of The Electrochemical Society, Vol. 166, Issue 10 https://doi.org/10.1149/2.0611910jes	journal	January 2019
Communication—Tris(bipyridyl)iron Complexes for High-Voltage Aqueous Redox Flow Batteries Ruan, Wenqing; Mao, Jiatao; Yang, Shida Journal of The Electrochemical Society, Vol. 167, Issue 10 https://doi.org/10.1149/1945-7111/ab9cc8	journal	June 2020
Alkaline Benzoquinone Aqueous Flow Battery for Large-Scale Storage of Electrical Energy Yang, Zhengjin; Tong, Liuchuan; Tabor, Daniel P. Advanced Energy Materials, Vol. 8, Issue 8 https://doi.org/10.1002/aenm.201702056	journal	December 2017
Alkaline Quinone Flow Battery with Long Lifetime at pH 12 Kwabi, David G.; Lin, Kaixiang; Ji, Yunlong Joule, Vol. 2, Issue 9 https://doi.org/10.1016/j.joule.2018.07.005	journal	September 2018
Extending the Lifetime of Organic Flow Batteries via Redox State Management Goulet, Marc-Antoni; Tong, Liuchuan; Pollack, Daniel A. Journal of the American Chemical Society https://doi.org/10.1021/jacs.8b13295	journal	April 2019
Unprecedented Capacity and Stability of Ammonium Ferrocyanide Catholyte in pH Neutral Aqueous Redox Flow Batteries Luo, Jian; Hu, Bo; Debruler, Camden Joule, Vol. 3, Issue 1 https://doi.org/10.1016/j.joule.2018.10.010	journal	January 2019
Electrolyte Lifetime in Aqueous Organic Redox Flow Batteries: A Critical Review Kwabi, David G.; Ji, Yunlong; Aziz, Michael J. Chemical Reviews, Vol. 120, Issue 14 https://doi.org/10.1021/acs.chemrev.9b00599	journal	February 2020
A metal-free organic–inorganic aqueous flow battery Huskinson, Brian; Marshak, Michael P.; Suh, Changwon Nature, Vol. 505, Issue 7482, p. 195-198 https://doi.org/10.1038/nature12909	journal	January 2014

Similar Records

Highly Stable, Low Redox Potential Quinone for Aqueous Flow Batteries**

Journal Article · Thu Feb 24 00:00:00 EST 2022 · Batteries & Supercaps · OSTI ID:1992956

Wu, Min; Bahari, Meisam; Jing, Yan; +5 more

High-Throughput Electrochemical Characterization of Aqueous Organic Redox Flow Battery Active Material

Journal Article · Mon Oct 09 00:00:00 EDT 2023 · Journal of the Electrochemical Society · OSTI ID:1992956

Fell, Eric M.; Aziz, Michael J.

An Aqueous Redox Flow Battery Based on Neutral Alkali Metal Ferri/ferrocyanide and Polysulfide Electrolytes

Journal Article · Fri Nov 13 00:00:00 EST 2015 · Journal of the Electrochemical Society, 163(1):A5150-A5153 · OSTI ID:1992956

Wei, Xiaoliang; Xia, Gordon; Kirby, Brent W.; +7 more

Title: Long-Term Stability of Ferri-/Ferrocyanide as an Electroactive Component for Redox Flow Battery Applications: On the Origin of Apparent Capacity Fade

Citation Formats

References (65)

Similar Records

Related Subjects