Revitalizing Iron Redox by Anion-Insertion-Assisted Ferro- and Ferri-Hydroxides Conversion at Low Alkalinity

Guo, Fenghua; Jagadeesan, Sathya Narayanan; Pidathala, Ranga Teja; Kim, SaeWon; Shan, Xiaoqiang; Deskins, Nathaniel Aaron; Abeykoon, A. M. Milinda; Kwon, Gihan; Olds, Daniel; Narayanan, Badri; Teng, Xiaowei

doi:10.1021/jacs.2c03113

Title: Revitalizing Iron Redox by Anion-Insertion-Assisted Ferro- and Ferri-Hydroxides Conversion at Low Alkalinity

Journal Article · 14 June 2022 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.2c03113 · OSTI ID:2281572

Guo, Fenghua ^[1]; Jagadeesan, Sathya Narayanan ^[1]; Pidathala, Ranga Teja ^[2]; Kim, SaeWon ^[1];

^[1];

^[3]; Abeykoon, A. M. Milinda ^[4];

^[4]; Olds, Daniel ^[4]; Narayanan, Badri ^[2]; Teng, Xiaowei ^[1]

Univ. of New Hampshire, Durham, NH (United States)
Univ. of Louisville, KY (United States)
Worcester Polytechnic Institute, MA (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)

Iron hydroxides are desirable alkaline battery electrodes for low cost and environmental beneficence. However, hydrogen evolution on charging and Fe₃O₄ formation on discharging cause low storage capacity and poor cycling life. Here, we report that green rust (GR) (Fe²⁺₄Fe³⁺₂ (HO^–)₁₂SO₄), formed via sulfate insertion, promotes Fe(OH)₂/FeOOH conversion and shows a discharge capacity of ~211 mAh g^–1 in half-cells and Coulombic efficiency of 93% after 300 cycles in full-cells. Theoretical calculations show that Fe(OH)₂/FeOOH conversion is facilitated by intercalated sulfate anions. Classical molecular dynamics simulations reveal that electrolyte alkalinity strongly impacts the energetics of sulfate solvation, and low alkalinity ensures fast transport of sulfate ions. Anion-insertion-assisted Fe(OH)₂/FeOOH conversion, also achieved with Cl^– ion, paves a pathway toward efficient utilization of Fe-based electrodes for sustainable applications.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: SC0012704; SC0018922; SC0021257; AC02-05CH11231

OSTI ID:: 2281572

Report Number(s):: BNL--225186-2024-JAAM

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 27 Vol. 144; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (24)

A Rechargeable Battery with an Iron Metal Anode Wu, Xianyong; Markir, Aaron; Xu, Yunkai Advanced Functional Materials, Vol. 29, Issue 20 https://doi.org/10.1002/adfm.201900911	journal	March 2019
The nickel/iron battery Chakkaravarthy, C.; Periasamy, P.; Jegannathan, S. Journal of Power Sources, Vol. 35, Issue 1 https://doi.org/10.1016/0378-7753(91)80002-F	journal	June 1991
Nickel/iron batteries Shukla, A. K.; Ravikumar, M. K.; Balasubramanian, T. S. Journal of Power Sources, Vol. 51, Issue 1-2 https://doi.org/10.1016/0378-7753(94)01953-3	journal	August 1994
Structure of the Fe(II-III) layered double hydroxysulphate green rust two from Rietveld analysis Simon, Lilian; François, Michel; Refait, Philippe Solid State Sciences, Vol. 5, Issue 2 https://doi.org/10.1016/S1293-2558(02)00019-5	journal	February 2003
An aqueous alkaline battery consisting of inexpensive all-iron redox chemistries for large-scale energy storage Wei, L.; Wu, M. C.; Zhao, T. S. Applied Energy, Vol. 215 https://doi.org/10.1016/j.apenergy.2018.01.080	journal	April 2018
Strong correlations between structural order and passive state at water–copper oxide interfaces Narayanan, Badri; Deshmukh, Sanket A.; Sankaranarayanan, Subramanian K. R. S. Electrochimica Acta, Vol. 179 https://doi.org/10.1016/j.electacta.2015.03.221	journal	October 2015
Magnetite and Green Rust: Synthesis, Properties, and Environmental Applications of Mixed-Valent Iron Minerals Usman, M.; Byrne, J. M.; Chaudhary, A. Chemical Reviews, Vol. 118, Issue 7 https://doi.org/10.1021/acs.chemrev.7b00224	journal	February 2018
Thermodynamic Equilibria in Aqueous Suspensions of Synthetic and Natural Fe(II)−Fe(III) Green Rusts: Occurrences of the Mineral in Hydromorphic Soils Génin, Jean-Marie R.; Bourrié, Guilhem; Trolard, Fabienne Environmental Science & Technology, Vol. 32, Issue 8 https://doi.org/10.1021/es970547m	journal	April 1998
Self-Assembled Monolayers of n -Alkanethiols Suppress Hydrogen Evolution and Increase the Efficiency of Rechargeable Iron Battery Electrodes Malkhandi, Souradip; Yang, Bo; Manohar, Aswin K. Journal of the American Chemical Society, Vol. 135, Issue 1 https://doi.org/10.1021/ja3095119	journal	December 2012
A Flexible Alkaline Rechargeable Ni/Fe Battery Based on Graphene Foam/Carbon Nanotubes Hybrid Film Liu, Jilei; Chen, Minghua; Zhang, Lili Nano Letters, Vol. 14, Issue 12 https://doi.org/10.1021/nl503852m	journal	November 2014
Low-crystalline iron oxide hydroxide nanoparticle anode for high-performance supercapacitors Owusu, Kwadwo Asare; Qu, Longbing; Li, Jiantao Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms14264	journal	March 2017
An ultrafast nickel–iron battery from strongly coupled inorganic nanoparticle/nanocarbon hybrid materials Wang, Hailiang; Liang, Yongye; Gong, Ming Nature Communications, Vol. 3, Issue 1 https://doi.org/10.1038/ncomms1921	journal	January 2012
Solvation and ion-pairing properties of the aqueous sulfate anion: explicit versus effective electronic polarization Pegado, Luís; Marsalek, Ondrej; Jungwirth, Pavel Physical Chemistry Chemical Physics, Vol. 14, Issue 29 https://doi.org/10.1039/c2cp40711f	journal	January 2012
A first principles study on the solvation and structure of SO[sub 4][sup 2−](H[sub 2]O)[sub n], n=6–12 Gao, Bing; Liu, Zhi-feng The Journal of Chemical Physics, Vol. 121, Issue 17 https://doi.org/10.1063/1.1802011	journal	January 2004
Structure of sodium sulphate aqueous solution/quartz interface: a molecular dynamics simulation Ma, Yi-Min; Zhang, Hui; Zhang, Bing-Jian Molecular Simulation, Vol. 40, Issue 7-9 https://doi.org/10.1080/08927022.2013.838676	journal	February 2014
Fast and Slow Dynamics of Hydrogen Bonds in Liquid Water Starr, Francis W.; Nielsen, Johannes K.; Stanley, H. Eugene Physical Review Letters, Vol. 82, Issue 11 https://doi.org/10.1103/PhysRevLett.82.2294	journal	March 1999
VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data Momma, Koichi; Izumi, Fujio Journal of Applied Crystallography, Vol. 44, Issue 6 https://doi.org/10.1107/S0021889811038970	journal	October 2011
GSAS-II : the genesis of a modern open-source all purpose crystallography software package Toby, Brian H.; Von Dreele, Robert B. Journal of Applied Crystallography, Vol. 46, Issue 2 https://doi.org/10.1107/S0021889813003531	journal	March 2013
Structure locale de δ-FeOOH Patrat, G.; de Bergevin, F.; Pernet, M. Acta Crystallographica Section B Structural Science, Vol. 39, Issue 2 https://doi.org/10.1107/S0108768183002232	journal	April 1983
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
High Performance Iron Electrodes with Metal Sulfide Additives Mitra, D.; Rajan, A. Sundar; Irshad, Ahamed Journal of The Electrochemical Society, Vol. 168, Issue 3 https://doi.org/10.1149/1945-7111/abe9c7	journal	March 2021
A High-Performance Rechargeable Iron Electrode for Large-Scale Battery-Based Energy Storage Manohar, Aswin K.; Malkhandi, Souradip; Yang, Bo Journal of The Electrochemical Society, Vol. 159, Issue 8 https://doi.org/10.1149/2.034208jes	journal	January 2012
The Role of Sulfide Additives in Achieving Long Cycle Life Rechargeable Iron Electrodes in Alkaline Batteries Manohar, Aswin K.; Yang, Chenguang; Narayanan, S. R. Journal of The Electrochemical Society, Vol. 162, Issue 9 https://doi.org/10.1149/2.0741509jes	journal	January 2015
Thermodynamics of Fe oxides: Part I. Entropy at standard temperature and pressure and heat capacity of goethite (α-FeOOH), lepidocrocite (γ-FeOOH), and maghemite (γ-Fe ₂ O ₃ ) Majzlan, Juraj; Lang, Brian E.; Stevens, Rebecca American Mineralogist, Vol. 88, Issue 5-6 https://doi.org/10.2138/am-2003-5-613	journal	May 2003

Similar Records

Chloride Insertion Enhances the Electrochemical Oxidation of Iron Hydroxide Double-Layer Hydroxide into Oxyhydroxide in Alkaline Iron Batteries

Journal Article · 2023 · Chemistry of Materials · OSTI ID:2281571

Jagadeesan, Sathya Narayanan; Barbosa, Gabriel D.; Guo, Fenghua; +6 more

Unlocking High Capacity and Reversible Alkaline Iron Redox Using Silicate-Sodium Hydroxide Hybrid Electrolytes

Journal Article · 2024 · ChemSusChem · OSTI ID:2440606

Jagadeesan, Sathya Narayanan; Guo, Fenghua; Pidathala, Ranga Teja; +5 more

Kagomé lattices as cathode: Effect of particle size and fluoride substitution on electrochemical lithium insertion in sodium- and ammonium Jarosites

Journal Article · 2016 · Journal of Solid State Chemistry · OSTI ID:22658058

Sandineni, Prashanth; Yaghoobnejad Asl, Hooman; Choudhury, Amitava

Related Subjects

36 MATERIALS SCIENCE
anions
basicity
electrolytes
evolution reactions
solvation

Title: Revitalizing Iron Redox by Anion-Insertion-Assisted Ferro- and Ferri-Hydroxides Conversion at Low Alkalinity

Citation Formats

References (24)

Similar Records

Related Subjects