DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Understanding the nanoscale redox-behavior of iron-anodes for rechargeable iron-air batteries

Abstract

Iron-air cells provide a promising and resource-efficient alternative battery concept with superior area specific power density characteristics compared to state-of-the-art Li-air batteries and potentially superior energy density characteristics compared to present Li-ion batteries. Understanding charge-transfer reactions at the anode-electrolyte interface is the key to develop high-performance cells. By employing in-situ electrochemical atomic force microscopy (in-situ EC-AFM), in-depth insight into the electrochemically induced surface reaction processes on iron in concentrated alkaline electrolyte is obtained. The results highlight the formation and growth of the redox-layer on iron over the course of several oxidation/reduction cycles. By this means, a direct correlation between topography changes and the corresponding electrochemical reactions at the nanoscale could unambiguously be established. Here in this paper, the twofold character of the nanoparticulate redox-layer in terms of its passivating character and its contribution to the electrochemical reactions is elucidated. Furthermore, the evolution of single nanoparticles on the iron electrode surface is evaluated in unprecedented and artifact-free detail. Based on the dedicated topography analysis, a detailed structural model for the evolution of the redox-layer which is likewise elementary for corrosion science and battery research is derived.

Authors:
 [1];  [2];  [3];  [3];  [3]; ORCiD logo [2]
  1. Forschungszentrum Julich (Germany). Inst. for Energy and Climate Research-Fundamental Electrochemistry (IEK-9); RWTH Aachen Univ., Aachen (Germany). Inst. of Physical Chemistry
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)
  3. Forschungszentrum Julich (Germany). Inst. for Energy and Climate Research-Fundamental Electrochemistry (IEK-9)
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1407732
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Nano Energy
Additional Journal Information:
Journal Volume: 41; Journal Issue: C; Journal ID: ISSN 2211-2855
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 36 MATERIALS SCIENCE; Iron electrode; Iron-air battery; Nanoparticles; Passivation; Corrosion; In-situ EC-AFM

Citation Formats

Weinrich, Henning, Come, Jérémy, Tempel, Hermann, Kungl, Hans, Eichel, Rüdiger-A., and Balke, Nina. Understanding the nanoscale redox-behavior of iron-anodes for rechargeable iron-air batteries. United States: N. p., 2017. Web. doi:10.1016/j.nanoen.2017.10.023.
Weinrich, Henning, Come, Jérémy, Tempel, Hermann, Kungl, Hans, Eichel, Rüdiger-A., & Balke, Nina. Understanding the nanoscale redox-behavior of iron-anodes for rechargeable iron-air batteries. United States. https://doi.org/10.1016/j.nanoen.2017.10.023
Weinrich, Henning, Come, Jérémy, Tempel, Hermann, Kungl, Hans, Eichel, Rüdiger-A., and Balke, Nina. Tue . "Understanding the nanoscale redox-behavior of iron-anodes for rechargeable iron-air batteries". United States. https://doi.org/10.1016/j.nanoen.2017.10.023. https://www.osti.gov/servlets/purl/1407732.
@article{osti_1407732,
title = {Understanding the nanoscale redox-behavior of iron-anodes for rechargeable iron-air batteries},
author = {Weinrich, Henning and Come, Jérémy and Tempel, Hermann and Kungl, Hans and Eichel, Rüdiger-A. and Balke, Nina},
abstractNote = {Iron-air cells provide a promising and resource-efficient alternative battery concept with superior area specific power density characteristics compared to state-of-the-art Li-air batteries and potentially superior energy density characteristics compared to present Li-ion batteries. Understanding charge-transfer reactions at the anode-electrolyte interface is the key to develop high-performance cells. By employing in-situ electrochemical atomic force microscopy (in-situ EC-AFM), in-depth insight into the electrochemically induced surface reaction processes on iron in concentrated alkaline electrolyte is obtained. The results highlight the formation and growth of the redox-layer on iron over the course of several oxidation/reduction cycles. By this means, a direct correlation between topography changes and the corresponding electrochemical reactions at the nanoscale could unambiguously be established. Here in this paper, the twofold character of the nanoparticulate redox-layer in terms of its passivating character and its contribution to the electrochemical reactions is elucidated. Furthermore, the evolution of single nanoparticles on the iron electrode surface is evaluated in unprecedented and artifact-free detail. Based on the dedicated topography analysis, a detailed structural model for the evolution of the redox-layer which is likewise elementary for corrosion science and battery research is derived.},
doi = {10.1016/j.nanoen.2017.10.023},
journal = {Nano Energy},
number = C,
volume = 41,
place = {United States},
year = {Tue Oct 10 00:00:00 EDT 2017},
month = {Tue Oct 10 00:00:00 EDT 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 31 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Promise and reality of post-lithium-ion batteries with high energy densities
journal, March 2016


Beyond Lithium Ion Batteries
journal, January 2015

  • Luntz, Alan
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 2
  • DOI: 10.1021/jz502665r

Metal–air batteries: from oxygen reduction electrochemistry to cathode catalysts
journal, January 2012

  • Cheng, Fangyi; Chen, Jun
  • Chemical Society Reviews, Vol. 41, Issue 6, p. 2172-2192
  • DOI: 10.1039/c1cs15228a

Metal-Air Batteries with High Energy Density: Li-Air versus Zn-Air
journal, December 2010

  • Lee, Jang-Soo; Tai Kim, Sun; Cao, Ruiguo
  • Advanced Energy Materials, Vol. 1, Issue 1, p. 34-50
  • DOI: 10.1002/aenm.201000010

Singlet Oxygen Formation during the Charging Process of an Aprotic Lithium-Oxygen Battery
journal, May 2016

  • Wandt, Johannes; Jakes, Peter; Granwehr, Josef
  • Angewandte Chemie International Edition, Vol. 55, Issue 24
  • DOI: 10.1002/anie.201602142

A Critical Review of Li∕Air Batteries
journal, January 2012

  • Christensen, Jake; Albertus, Paul; Sanchez-Carrera, Roel S.
  • Journal of The Electrochemical Society, Vol. 159, Issue 2, p. R1-R30
  • DOI: 10.1149/2.086202jes

Towards greener and more sustainable batteries for electrical energy storage
journal, November 2014


The rechargeable revolution: A better battery
journal, March 2014


Recent developments in materials for aluminum–air batteries: A review
journal, December 2015

  • Mokhtar, Marliyana; Talib, Meor Zainal Meor; Majlan, Edy Herianto
  • Journal of Industrial and Engineering Chemistry, Vol. 32
  • DOI: 10.1016/j.jiec.2015.08.004

Study and development of non-aqueous silicon-air battery
journal, August 2010


Limitation of Discharge Capacity and Mechanisms of Air-Electrode Deactivation in Silicon-Air Batteries
journal, October 2012


Long run discharge, performance and efficiency of primary Silicon–air cells with alkaline electrolyte
journal, January 2017


Recent advances in zinc–air batteries
journal, January 2014


Materials challenges and technical approaches for realizing inexpensive and robust iron–air batteries for large-scale energy storage
journal, May 2012


Fe/carbon nanofiber composite materials for Fe–air battery anodes
journal, September 2013


A Review of the Iron-Air Secondary Battery for Energy Storage
journal, September 2014

  • McKerracher, R. D.; Ponce de Leon, Carlos; Wills, R. G. A.
  • ChemPlusChem, Vol. 80, Issue 2
  • DOI: 10.1002/cplu.201402238

A High-Performance Rechargeable Iron Electrode for Large-Scale Battery-Based Energy Storage
journal, January 2012

  • Manohar, Aswin K.; Malkhandi, Souradip; Yang, Bo
  • Journal of The Electrochemical Society, Vol. 159, Issue 8
  • DOI: 10.1149/2.034208jes

A Rechargeable, Aqueous Iron Air Battery with Nanostructured Electrodes Capable of High Energy Density Operation
journal, January 2017

  • Figueredo-Rodríguez, H. A.; McKerracher, R. D.; Insausti, M.
  • Journal of The Electrochemical Society, Vol. 164, Issue 6
  • DOI: 10.1149/2.0711706jes

The potentiodynamic behaviour of iron in alkaline solutions
journal, April 1979


The anodic dissolution process on active iron in alkaline solutions
journal, October 1982


Passivity of Iron in Alkaline Solutions Studied by In Situ XANES and a Laser Reflection Technique
journal, June 1999

  • Schmuki, P.; Büchler, M.; Virtanen, S.
  • Journal of The Electrochemical Society, Vol. 146, Issue 6
  • DOI: 10.1149/1.1391897

Passivity
book, November 2009


Passivity–the key to our metals-based civilization
journal, June 1999


Thin Oxide Films on Iron
journal, January 1974

  • Cohen, Morris
  • Journal of The Electrochemical Society, Vol. 121, Issue 6
  • DOI: 10.1149/1.2402379

In Situ X‐Ray Absorption Near Edge Structure Study of the Potential Dependence of the Formation of the Passive Film on Iron in Borate Buffer
journal, July 1997

  • Oblonsky, L. J.; Davenport, A. J.; Ryan, M. P.
  • Journal of The Electrochemical Society, Vol. 144, Issue 7
  • DOI: 10.1149/1.1837826

Stability and Growth of Passive Films on Pure Iron in Borate Buffer as Investigated by 18O/SIMS
journal, March 1987

  • Goetz, R.; Mitchell, D. F.; MacDougall, B.
  • Journal of The Electrochemical Society, Vol. 134, Issue 3
  • DOI: 10.1149/1.2100505

M�ssbauer spectroscopy investigation of the iron electrode during cycling in alkaline solution
journal, November 1975

  • Geronov, Y.; Tomov, T.; Georgiev, S.
  • Journal of Applied Electrochemistry, Vol. 5, Issue 4
  • DOI: 10.1007/BF00608799

First Stages of Electrochemical Growth of the Passive Film on Iron
journal, January 2001

  • Dı́ez-Pérez, I.; Gorostiza, P.; Sanz, F.
  • Journal of The Electrochemical Society, Vol. 148, Issue 8
  • DOI: 10.1149/1.1381073

In Situ X-Ray-Diffraction Studies of Passive Oxide Films
journal, July 1999


Nanoscale mapping of ion diffusion in a lithium-ion battery cathode
journal, August 2010


Electrochemistry at the Nanoscale: The Force Dimension
journal, January 2014

  • Black, J.; Strelcov, E.; Balke, N.
  • Interface magazine, Vol. 23, Issue 2
  • DOI: 10.1149/2.F06142if

Elucidating the Phase Transformation of Li 4 Ti 5 O 12 Lithiation at the Nanoscale
journal, March 2016


Synthesis of nano-Fe3O4-loaded tubular carbon nanofibers and their application as negative electrodes for Fe/air batteries
journal, October 2011


Calculations of electorn inelastic mean free paths. II. Data for 27 elements over the 50-2000 eV range
journal, December 1991

  • Tanuma, S.; Powell, C. J.; Penn, D. R.
  • Surface and Interface Analysis, Vol. 17, Issue 13
  • DOI: 10.1002/sia.740171304

The Passivity of Iron in the Presence of Ethylenediaminetetraacetic Acid I. General Electrochemical Behavior
journal, January 2000

  • Sikora, Elzbieta; Macdonald, Digby D.
  • Journal of The Electrochemical Society, Vol. 147, Issue 11
  • DOI: 10.1149/1.1394024

Slow Potentiodynamic Studies of Porous Alkaline Iron Electrodes
journal, June 1976

  • Andersson, Bo; Öjefors, Lars
  • Journal of The Electrochemical Society, Vol. 123, Issue 6
  • DOI: 10.1149/1.2132940

Reduction of magnetite to metallic iron in strong alkaline medium
journal, March 2016


Topology of Iron Surfaces in the Early Stages of Electrochemical Corrosion
journal, September 1992

  • Oelkrug, Dieter; Fritz, Martin; Stauch, Heinz
  • Journal of The Electrochemical Society, Vol. 139, Issue 9
  • DOI: 10.1149/1.2221242

Topological aspects of iron corrosion in alkaline solution by means of scanning force microscopy (SFM)
journal, May 1994


Theory, Production and Mechanism of Formation of Monodispersed Hydrosols
journal, November 1950

  • LaMer, Victor K.; Dinegar, Robert H.
  • Journal of the American Chemical Society, Vol. 72, Issue 11
  • DOI: 10.1021/ja01167a001

A generalized diffusion model for growth of nanoparticles synthesized by colloidal methods
journal, April 2014

  • Wen, Tianlong; Brush, Lucien N.; Krishnan, Kannan M.
  • Journal of Colloid and Interface Science, Vol. 419
  • DOI: 10.1016/j.jcis.2013.12.018

Works referencing / citing this record:

Impact of the charging conditions on the discharge performance of rechargeable iron-anodes for alkaline iron–air batteries
journal, February 2018

  • Weinrich, Henning; Gehring, Markus; Tempel, Hermann
  • Journal of Applied Electrochemistry, Vol. 48, Issue 4
  • DOI: 10.1007/s10800-018-1176-4

Silicon and Iron as Resource-Efficient Anode Materials for Ambient-Temperature Metal-Air Batteries: A Review
text, January 2019


Silicon and Iron as Resource-Efficient Anode Materials for Ambient-Temperature Metal-Air Batteries: A Review
journal, July 2019

  • Weinrich, Henning; Durmus, Yasin Emre; Tempel, Hermann
  • Materials, Vol. 12, Issue 13
  • DOI: 10.3390/ma12132134

Silicon and Iron as Resource-Efficient Anode Materials for Ambient-Temperature Metal-Air Batteries: A Review
text, January 2019