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Title: Electrochemical (de)lithiation of silver ferrite and composites: mechanistic insights from ex situ, in situ, and operando X-ray techniques

Abstract

Here, the structure of pristine AgFeO2 and phase makeup of Ag0.2FeO1.6 (a one-pot composite comprised of nanocrystalline stoichiometric AgFeO2 and amorphous γ-Fe2O3 phases) was investigated using synchrotron x-ray diffraction. A new stacking-fault model was proposed for AgFeO2 powder synthesized using the co-precipitation method. The lithiation/de-lithiation mechanisms of silver ferrite, AgFeO2 and Ag0.2FeO1.6 were investigated using ex-situ, in-situ, and operando characterization techniques. An amorphous γ-Fe2O3 component in the Ag0.2FeO1.6 sample is quantified. Operando XRD of electrochemically reduced AgFeO2 and Ag0.2FeO1.6 composites demonstrated differences in the structural evolution of the nanocrystalline AgFeO2 component. As complimentary techniques to XRD, ex-situ x-ray Absorption Spectroscopy (XAS) provided insight into the short-range structure of the (de)lithiated nanocrystalline electrodes, and a novel in-situ high energy x-ray fluorescence nanoprobe (HXN) mapping measurement was applied to spatially resolve the progression of discharge. Based on the results, a redox mechanism is proposed where the full reduction of Ag+ to Ag0 and partial reduction of Fe3+ to Fe2+ occur on reduction to 1.0 V, resulting in a Li1+yFeIIIFeIIyO2 phase. The Li1+yFeIIIFeIIyO2 phase can then reversibly cycle between Fe3+ and Fe2+ oxidation states, permitting good capacity retention over 50 cycles. In the Ag0.2FeO1.6 composite, a substantial amorphous γ-Fe2O3 component is observed whichmore » discharges to rock salt LiFe2O3 and Fe0 metal phase in the 3.5 – 1.0 V voltage range (in parallel with the AgFeO2 mechanism), and reversibly reoxidizes to a nanocrystalline iron oxide phase.« less

Authors:
 [1];  [2];  [1];  [3];  [3];  [2];  [4];  [1];  [1];  [4];  [4];  [4]; ORCiD logo [5];  [6]; ORCiD logo [6]
  1. Stony Brook Univ., NY (United States). Dept. of Chemistry
  2. Stony Brook Univ., NY (United States). Dept. of Materials Science and Engineering
  3. Brookhaven National Lab. (BNL), Upton, NY (United States). Energy Sciences Directorate
  4. Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
  5. Stony Brook Univ., NY (United States). Dept. of Chemistry; Stony Brook Univ., NY (United States). Dept. of Materials Science and Engineering; Brookhaven National Lab. (BNL), Upton, NY (United States). Energy Sciences Directorate
  6. Stony Brook Univ., NY (United States). Dept. of Chemistry; Stony Brook Univ., NY (United States). Dept. of Materials Science and Engineering
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1376184
Report Number(s):
BNL-114168-2017-JA
Journal ID: ISSN 1463-9076; PPCPFQ
Grant/Contract Number:  
SC0012704; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP
Additional Journal Information:
Journal Volume: 19; Journal Issue: 33; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Durham, Jessica L., Brady, Alexander B., Cama, Christina A., Bock, David C., Pelliccione, Christopher J., Zhang, Qing, Ge, Mingyuan, Li, Yue Ru, Zhang, Yiman, Yan, Hanfei, Huang, Xiaojing, Chu, Yong, Takeuchi, Esther S., Takeuchi, Kenneth J., and Marschilok, Amy C. Electrochemical (de)lithiation of silver ferrite and composites: mechanistic insights from ex situ, in situ, and operando X-ray techniques. United States: N. p., 2017. Web. doi:10.1039/C7CP04012A.
Durham, Jessica L., Brady, Alexander B., Cama, Christina A., Bock, David C., Pelliccione, Christopher J., Zhang, Qing, Ge, Mingyuan, Li, Yue Ru, Zhang, Yiman, Yan, Hanfei, Huang, Xiaojing, Chu, Yong, Takeuchi, Esther S., Takeuchi, Kenneth J., & Marschilok, Amy C. Electrochemical (de)lithiation of silver ferrite and composites: mechanistic insights from ex situ, in situ, and operando X-ray techniques. United States. https://doi.org/10.1039/C7CP04012A
Durham, Jessica L., Brady, Alexander B., Cama, Christina A., Bock, David C., Pelliccione, Christopher J., Zhang, Qing, Ge, Mingyuan, Li, Yue Ru, Zhang, Yiman, Yan, Hanfei, Huang, Xiaojing, Chu, Yong, Takeuchi, Esther S., Takeuchi, Kenneth J., and Marschilok, Amy C. Wed . "Electrochemical (de)lithiation of silver ferrite and composites: mechanistic insights from ex situ, in situ, and operando X-ray techniques". United States. https://doi.org/10.1039/C7CP04012A. https://www.osti.gov/servlets/purl/1376184.
@article{osti_1376184,
title = {Electrochemical (de)lithiation of silver ferrite and composites: mechanistic insights from ex situ, in situ, and operando X-ray techniques},
author = {Durham, Jessica L. and Brady, Alexander B. and Cama, Christina A. and Bock, David C. and Pelliccione, Christopher J. and Zhang, Qing and Ge, Mingyuan and Li, Yue Ru and Zhang, Yiman and Yan, Hanfei and Huang, Xiaojing and Chu, Yong and Takeuchi, Esther S. and Takeuchi, Kenneth J. and Marschilok, Amy C.},
abstractNote = {Here, the structure of pristine AgFeO2 and phase makeup of Ag0.2FeO1.6 (a one-pot composite comprised of nanocrystalline stoichiometric AgFeO2 and amorphous γ-Fe2O3 phases) was investigated using synchrotron x-ray diffraction. A new stacking-fault model was proposed for AgFeO2 powder synthesized using the co-precipitation method. The lithiation/de-lithiation mechanisms of silver ferrite, AgFeO2 and Ag0.2FeO1.6 were investigated using ex-situ, in-situ, and operando characterization techniques. An amorphous γ-Fe2O3 component in the Ag0.2FeO1.6 sample is quantified. Operando XRD of electrochemically reduced AgFeO2 and Ag0.2FeO1.6 composites demonstrated differences in the structural evolution of the nanocrystalline AgFeO2 component. As complimentary techniques to XRD, ex-situ x-ray Absorption Spectroscopy (XAS) provided insight into the short-range structure of the (de)lithiated nanocrystalline electrodes, and a novel in-situ high energy x-ray fluorescence nanoprobe (HXN) mapping measurement was applied to spatially resolve the progression of discharge. Based on the results, a redox mechanism is proposed where the full reduction of Ag+ to Ag0 and partial reduction of Fe3+ to Fe2+ occur on reduction to 1.0 V, resulting in a Li1+yFeIIIFeIIyO2 phase. The Li1+yFeIIIFeIIyO2 phase can then reversibly cycle between Fe3+ and Fe2+ oxidation states, permitting good capacity retention over 50 cycles. In the Ag0.2FeO1.6 composite, a substantial amorphous γ-Fe2O3 component is observed which discharges to rock salt LiFe2O3 and Fe0 metal phase in the 3.5 – 1.0 V voltage range (in parallel with the AgFeO2 mechanism), and reversibly reoxidizes to a nanocrystalline iron oxide phase.},
doi = {10.1039/C7CP04012A},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 33,
volume = 19,
place = {United States},
year = {Wed Aug 02 00:00:00 EDT 2017},
month = {Wed Aug 02 00:00:00 EDT 2017}
}

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Works referenced in this record:

Electrochemical Reduction of Silver Vanadium Phosphorus Oxide, Ag 2 VO 2 PO 4 : The Formation of Electrically Conductive Metallic Silver Nanoparticles
journal, October 2009

  • Takeuchi, Esther S.; Marschilok, Amy C.; Tanzil, Kevin
  • Chemistry of Materials, Vol. 21, Issue 20
  • DOI: 10.1021/cm902102k

ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005


Ultrasound assisted ambient temperature synthesis of ternary oxide AgMO2 (M=Fe, Ga)
journal, June 2009


Magnetosomes could be protective shields against metal stress in magnetotactic bacteria
journal, July 2020


Heterogeneous behaviour of the lithium battery composite electrode LiFePO4
journal, May 2013


Zur Kenntnis der ?Ferrate(III)? M'FeO2 des einwertigen Ag, Cu und Tl
journal, August 1968

  • Gessner, Wolfgang
  • Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 360, Issue 5-6
  • DOI: 10.1002/zaac.19683600504

Surface-modified maghemite as the cathode material for lithium batteries
journal, October 2008


Impact of Multifunctional Bimetallic Materials on Lithium Battery Electrochemistry
journal, August 2016

  • Durham, Jessica L.; Poyraz, Altug S.; Takeuchi, Esther S.
  • Accounts of Chemical Research, Vol. 49, Issue 9
  • DOI: 10.1021/acs.accounts.6b00318

Ab initio curved-wave x-ray-absorption fine structure
journal, September 1991


In situ visualization of Li/Ag2VP2O8 batteries revealing rate-dependent discharge mechanism
journal, January 2015


Effect of chemical oxidation for nano-size γ-Fe2O3 as lithium battery cathode
journal, February 2007


Silver vanadium phosphorous oxide, Ag2VO2PO4: Chimie douce preparation and resulting lithium cell electrochemistry
journal, August 2011


GSAS-II : the genesis of a modern open-source all purpose crystallography software package
journal, March 2013


Silver vanadium oxides and related battery applications
journal, October 2001


Transport properties and lithium insertion study in the p-type semi-conductors AgCuO2 and AgCu0.5Mn0.5O2
journal, February 2009

  • Sauvage, F.; Muñoz-Rojas, D.; Poeppelmeier, K. R.
  • Journal of Solid State Chemistry, Vol. 182, Issue 2
  • DOI: 10.1016/j.jssc.2008.10.038

Determination of crystallite size in a magnetic nanocomposite using extended x-ray absorption fine structure
journal, July 2003

  • Calvin, S.; Miller, M. M.; Goswami, R.
  • Journal of Applied Physics, Vol. 94, Issue 1
  • DOI: 10.1063/1.1581344

Pushing the limits: an instrument for hard X-ray imaging below 20 nm
journal, January 2015


Oxygen intercalation of two polymorphs of CuScO2
journal, August 2004


Hydrothermal Synthesis of Delafossite-Type Oxides
journal, March 2006

  • Sheets, William C.; Mugnier, Emmanuelle; Barnabe, Antoine
  • ChemInform, Vol. 37, Issue 11
  • DOI: 10.1002/chin.200611236

Solid-State Synthesis and Characterization of Silver Vanadium Oxide for Use as a Cathode Material for Lithium Batteries
journal, April 1994

  • Leising, Randolph A.; Takeuchi, Esther Sans
  • Chemistry of Materials, Vol. 6, Issue 4
  • DOI: 10.1021/cm00040a025

Crystallographic data for pure crystalline silver ferrite
journal, March 1964


Chemistry of noble metal oxides. II. Crystal structures of platinum cobalt dioxide, palladium cobalt dioxide, coppper iron dioxide, and silver iron dioxide
journal, April 1971

  • Shannon, Robert D.; Prewitt, Charles T.; Rogers, Donald Burl
  • Inorganic Chemistry, Vol. 10, Issue 4
  • DOI: 10.1021/ic50098a012

Theoretical x-ray absorption fine structure standards
journal, July 1991

  • Rehr, J. J.; Mustre de Leon, J.; Zabinsky, S. I.
  • Journal of the American Chemical Society, Vol. 113, Issue 14
  • DOI: 10.1021/ja00014a001

XLI. Precision measurements of crystal parameters
journal, February 1933

  • Owen, E. A.; Yates, E. L.
  • The London, Edinburgh, and Dublin Philosophical Magazine and Journal of Science, Vol. 15, Issue 98
  • DOI: 10.1080/14786443309462199

The crystal structure of a new hexagonal phase of AgFeO2
journal, June 1972

  • Okamoto, S.; Okamoto, S. I.; Ito, T.
  • Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 28, Issue 6
  • DOI: 10.1107/S056774087200500X

Silver ferrite/maghemite composites and mixtures: Impact of one-pot composite preparation on battery-relevant electrochemistry
journal, March 2018


The lattice expansion of iron
journal, May 1955

  • Basinski, Zbigniew Stanislaw; Hume-Rothery, William; Sutton, A. L.
  • Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences, Vol. 229, Issue 1179, p. 459-467
  • DOI: 10.1098/rspa.1955.0102

Synthesis and characterization of nano silver ferrite composite
journal, July 2010

  • Murthy, Y. L. N.; Kondala Rao, T.; Kasi viswanath, I. V.
  • Journal of Magnetism and Magnetic Materials, Vol. 322, Issue 14
  • DOI: 10.1016/j.jmmm.2010.01.036

Operando X-ray Absorption Spectroscopy Study of Atomic Phase Reversibility with Wavelet Transform in the Lithium-Rich Manganese Based Oxide Cathode
journal, June 2016


Battery Relevant Electrochemistry of Ag 7 Fe 3 (P 2 O 7 ) 4 : Contrasting Contributions from the Redox Chemistries of Ag + and Fe 3+
journal, October 2016


Polydopamine functionalized graphene/NiFe2O4 nanocomposite with improving Li storage performances
journal, May 2014


A General Recursion Method for Calculating Diffracted Intensities from Crystals Containing Planar Faults
journal, June 1991

  • Treacy, M. M. J.; Newsam, J. M.; Deem, M. W.
  • Proceedings of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 433, Issue 1889
  • DOI: 10.1098/rspa.1991.0062

Formation of AgFeO2, α-FeOOH, and Ag2O from mixed Fe(NO3)3–AgNO3 solutions at high pH
journal, July 2013


Hydrothermal Synthesis of Delafossite-Type Oxides
journal, January 2006

  • Sheets, William C.; Mugnier, Emmanuelle; Barnabé, Antoine
  • Chemistry of Materials, Vol. 18, Issue 1
  • DOI: 10.1021/cm051791c

Hollow Iron Oxide Nanoparticles for Application in Lithium Ion Batteries
journal, April 2012

  • Koo, Bonil; Xiong, Hui; Slater, Michael D.
  • Nano Letters, Vol. 12, Issue 5, p. 2429-2435
  • DOI: 10.1021/nl3004286

Nickel ferrite as a stable, high capacity and high rate anode for Li-ion battery applications
journal, January 2013


Physicochemical characterization of CuFeO2 and lithium intercalation
journal, February 2000


A facile bubble-assisted synthesis of porous Zn ferrite hollow microsphere and their excellent performance as an anode in lithium ion battery
journal, March 2013

  • Yao, Lingmin; Hou, Xianhua; Hu, Shejun
  • Journal of Solid State Electrochemistry, Vol. 17, Issue 7
  • DOI: 10.1007/s10008-013-2069-4

Über Silberferrite. I. Mitteilung: Silberferrite aus Ortho- und Meta-Ferrihydroxyd
journal, April 1931

  • Krause, Alfons; Pilawski, K.
  • Zeitschrift für anorganische und allgemeine Chemie, Vol. 197, Issue 1
  • DOI: 10.1002/zaac.19311970129

Conversion mechanisms of cobalt oxide anode for Li-ion battery: In situ X-ray absorption fine structure studies
journal, January 2015


The infrared dielectric properties of maghemite, ?-Fe2O3, from reflectance measurement on pressed powders
journal, February 1995

  • Pecharrom�n, Carlos; Gonz�lez-Carre�o, T.; Iglesias, JuanE.
  • Physics and Chemistry of Minerals, Vol. 22, Issue 1
  • DOI: 10.1007/BF00202677

Electrochemical reduction of silver vanadium phosphorous oxide, Ag2VO2PO4: Silver metal deposition and associated increase in electrical conductivity
journal, October 2010


Synthesis and Electrochemistry of Silver Ferrite
journal, January 2011

  • Farley, K. E.; Marschilok, A. C.; Takeuchi, E. S.
  • Electrochemical and Solid-State Letters, Vol. 15, Issue 2
  • DOI: 10.1149/2.010202esl

Redox chemistry of a binary transition metal oxide (AB 2 O 4 ): a study of the Cu 2+ /Cu 0 and Fe 3+ /Fe 0 interconversions observed upon lithiation in a CuFe 2 O 4 battery using X-ray absorption spectroscopy
journal, January 2016

  • Cama, Christina A.; Pelliccione, Christopher J.; Brady, Alexander B.
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 25
  • DOI: 10.1039/C6CP02974D

Comparison of extended x-ray absorption fine structure and Scherrer analysis of x-ray diffraction as methods for determining mean sizes of polydisperse nanoparticles
journal, December 2005

  • Calvin, S.; Luo, S. X.; Caragianis-Broadbridge, C.
  • Applied Physics Letters, Vol. 87, Issue 23
  • DOI: 10.1063/1.2137872

MnFe2O4–graphene nanocomposites with enhanced performances as anode materials for Li-ion batteries
journal, January 2013

  • Xiao, Yinglin; Zai, Jiantao; Tao, Liqi
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 11
  • DOI: 10.1039/c3cp50220a

Multimodality hard-x-ray imaging of a chromosome with nanoscale spatial resolution
journal, February 2016

  • Yan, Hanfei; Nazaretski, Evgeny; Lauer, Kenneth
  • Scientific Reports, Vol. 6, Issue 1
  • DOI: 10.1038/srep20112

High capacity and high rate capability of nanostructured CuFeO2 anode materials for lithium-ion batteries
journal, August 2011


Microwave synthesis of high-quality and uniform 4 nm ZnFe 2 O 4 nanocrystals for application in energy storage and nanomagnetics
journal, January 2016

  • Suchomski, Christian; Breitung, Ben; Witte, Ralf
  • Beilstein Journal of Nanotechnology, Vol. 7
  • DOI: 10.3762/bjnano.7.126

Synthetic control of composition and crystallite size of silver ferrite composites: profound electrochemistry impacts
journal, January 2015

  • Durham, Jessica L.; Kirshenbaum, Kevin; Takeuchi, Esther S.
  • Chemical Communications, Vol. 51, Issue 24
  • DOI: 10.1039/C4CC10277K

Nanocrystalline Iron Oxides Prepared via Co-Precipitation for Lithium Battery Cathode Applications
journal, August 2015

  • Durham, J.; Takeuchi, E. S.; Marschilok, A. C.
  • ECS Transactions, Vol. 66, Issue 9
  • DOI: 10.1149/06609.0111ecst

Electrochemical and In Situ XAFS-XRD Investigation of Nb[sub 2]O[sub 5] for Rechargeable Lithium Batteries
journal, January 2006

  • Kodama, Ryoji; Terada, Yasuko; Nakai, Izumi
  • Journal of The Electrochemical Society, Vol. 153, Issue 3
  • DOI: 10.1149/1.2163788

Crystallographic Data 186. Lithium
journal, December 1959

  • Nadler, M. R/.; Kempier, C. P.
  • Analytical Chemistry, Vol. 31, Issue 12
  • DOI: 10.1021/ac60156a007

IFEFFIT  : interactive XAFS analysis and FEFF fitting
journal, March 2001


Theoretical approaches to x-ray absorption fine structure
journal, July 2000


11 nm hard X-ray focus from a large-aperture multilayer Laue lens
journal, December 2013

  • Huang, Xiaojing; Yan, Hanfei; Nazaretski, Evgeny
  • Scientific Reports, Vol. 3, Issue 1
  • DOI: 10.1038/srep03562

EXAFS as a tool to interrogate the size and shape of mono and bimetallic catalyst nanoparticles
journal, January 2010

  • Beale, Andrew M.; Weckhuysen, Bert M.
  • Physical Chemistry Chemical Physics, Vol. 12, Issue 21
  • DOI: 10.1039/b925206a

An X‐Ray Study of the Wüstite (FeO) Solid Solutions
journal, January 1933

  • Jette, Eric R.; Foote, Frank
  • The Journal of Chemical Physics, Vol. 1, Issue 1
  • DOI: 10.1063/1.1749215