Structural Analysis of K4Fe(CN)6·3H2O, K3Fe(CN)6 and Prussian Blue

Mansour, Azzam N.; Ko, Jonathan K.; Waller, Gordon H.; Martin, Curtis A.; Zhang, Chen; Qiao, Xiaoyao; Wang, Yuchen; Zhou, Xiangyang; Balasubramanian, Mahalingam

doi:10.1149/2162-8777/ac2591

Structural Analysis of K₄Fe(CN)₆·3H₂O, K₃Fe(CN)₆ and Prussian Blue

Journal Article · Fri Oct 01 00:00:00 EDT 2021 · ECS Journal of Solid State Science and Technology

DOI:https://doi.org/10.1149/2162-8777/ac2591· OSTI ID:1842289

Mansour, Azzam N. ^[1]; Ko, Jonathan K. ^[1]; Waller, Gordon H. ^[1]; Martin, Curtis A. ^[1]; Zhang, Chen ^[2]; Qiao, Xiaoyao ^[2]; Wang, Yuchen ^[2]; ^[2]; Balasubramanian, Mahalingam ^[3]

Naval Surface Warfare Center, Carderock Division, West Bethesda, MD (United States)
University of Miami, Coral Gables, FL (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

XRD and XAS were used to characterize the bulk structure, while XPS was used to characterize the surface structure, of commercially obtained nominally K₄Fe(CN)₆·3H₂O, K₃Fe(CN)₆ and our synthesized Prussian Blue (PB) material. K₄Fe(CN)₆·3H₂O was found to consist of a fully hydrated phase, which crystallizes in the monoclinic form and a less hydrated or anhydrous phase which crystallizes in the orthorhombic form. K₃Fe(CN)₆ was found to consist of the well-established orthorhombic form rather than the monoclinic form. The structure of our synthesized Prussian Blue (PB) was found to be consistent with that reported for (KOH)^0.7Fe(III)_1.33Fe(II)(CN)₆·4.0H₂O which crystallizes in the cubic form. XPS and XAS confirmed the presence of ferrous Fe(II) at the surface and bulk levels in K₄Fe(CN)₆·xH₂O. However, XPS revealed the presence of Fe(II) (~30%) and Fe(III) (~70%) in the surface region of K₃Fe(CN)₆ while XAS confirmed the presence of mostly Fe(III) at the bulk level. Both XPS and XANES confirmed the presence of Fe(II) and Fe(III) in the surface and bulk regions of PB. We report that this ex situ XAS study will be used to support the analysis of an in situ XAS data collected on a PB containing supercapacitor to understand the mechanistic origin of pseudocapacitance in these devices.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: Office of Naval Research (ONR); USDOE Office of Science (SC)

Grant/Contract Number:: AC02-06CH11357; AC05-00OR22725

OSTI ID:: 1842289

Alternate ID(s):: OSTI ID: 1824687
OSTI ID: 1825770

Journal Information:: ECS Journal of Solid State Science and Technology, Journal Name: ECS Journal of Solid State Science and Technology Journal Issue: 10 Vol. 10; ISSN 2162-8769

Publisher:: Electrochemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (44)

Supercapacitors Performance Evaluation Zhang, Sanliang; Pan, Ning Advanced Energy Materials, Vol. 5, Issue 6 https://doi.org/10.1002/aenm.201401401	journal	December 2014
The Emerging Chemistry of Sodium Ion Batteries for Electrochemical Energy Storage Kundu, Dipan; Talaie, Elahe; Duffort, Victor Angewandte Chemie International Edition, Vol. 54, Issue 11 https://doi.org/10.1002/anie.201410376	journal	February 2015
X-ray photoelectron and mössbauer spectroscopy on a variety of iron compounds Johansson, L. Y.; Larsson, R.; Blomquist, J. Chemical Physics Letters, Vol. 24, Issue 4 https://doi.org/10.1016/0009-2614(74)80166-1	journal	February 1974
Size effect of powdered sample on EXAFS amplitude Lu, Kun-quan; Stern, E. A. Nuclear Instruments and Methods in Physics Research, Vol. 212, Issue 1-3 https://doi.org/10.1016/0167-5087(83)90730-5	journal	July 1983
Use of X-ray photoelectron and Mössbauer spectroscopies in the study of iron pentacyanide complexes Yatsimirskii, K. B.; Nemoshkalenko, V. V.; Nazarenko, Yu. P. Journal of Electron Spectroscopy and Related Phenomena, Vol. 10, Issue 3 https://doi.org/10.1016/0368-2048(77)85023-8	journal	January 1977
Kinetics of photoreduction of Fe(III) in solid solution K3(Fe,M)(CN)6 (where M is Cr, Co) during XPS measurement Oku, Masaoki Journal of Electron Spectroscopy and Related Phenomena, Vol. 67, Issue 3 https://doi.org/10.1016/0368-2048(93)02044-M	journal	June 1994
Ultracapacitors: why, how, and where is the technology Burke, Andrew Journal of Power Sources, Vol. 91, Issue 1, p. 37-50 https://doi.org/10.1016/S0378-7753(00)00485-7	journal	November 2000
Facile synthesis of cobalt hexacyanoferrate/graphene nanocomposites for high-performance supercapacitor Wang, Jian-Gan; Zhang, Zhiyong; Liu, Xingrui Electrochimica Acta, Vol. 235 https://doi.org/10.1016/j.electacta.2017.03.094	journal	May 2017
Prussian blue and its derivatives as electrode materials for electrochemical energy storage Xu, Yuxia; Zheng, Shasha; Tang, Hanfei Energy Storage Materials, Vol. 9 https://doi.org/10.1016/j.ensm.2017.06.002	journal	October 2017
Effect of NaI/I2 mediators on properties of PEO/LiAlO2 based all-solid-state supercapacitors Yin, Yijing; Zhou, Juanjuan; Mansour, Azzam N. Journal of Power Sources, Vol. 196, Issue 14 https://doi.org/10.1016/j.jpowsour.2011.02.079	journal	July 2011
Development of all-solid-state mediator-enhanced supercapacitors with polyvinylidene fluoride/lithium trifluoromethanesulfonate separators Zhou, Juanjuan; Cai, Jinshu; Cai, Sirui Journal of Power Sources, Vol. 196, Issue 23 https://doi.org/10.1016/j.jpowsour.2011.08.051	journal	December 2011
X-ray absorption spectroscopic study of sodium iodide and iodine mediators in a solid-state supercapacitor Mansour, Azzam N.; Zhou, Juanjuan; Zhou, Xiangyang Journal of Power Sources, Vol. 245 https://doi.org/10.1016/j.jpowsour.2013.06.129	journal	January 2014
Characterizing rapid capacity fade and impedance evolution in high rate pulsed discharged lithium iron phosphate cells for complex, high power loads Wong, Derek N.; Wetz, David A.; Heinzel, John M. Journal of Power Sources, Vol. 328 https://doi.org/10.1016/j.jpowsour.2016.08.013	journal	October 2016
Electronic effects of metal hexacyanoferrates: An XPS and FTIR study Gerber, Stefaans J.; Erasmus, E. Materials Chemistry and Physics, Vol. 203 https://doi.org/10.1016/j.matchemphys.2017.09.029	journal	January 2018
Preparation of cobalt hexacyanoferrate nanowires using carbon nanotubes as templates Qian, L.; Yang, X. Talanta, Vol. 69, Issue 4 https://doi.org/10.1016/j.talanta.2005.11.053	journal	June 2006
Aqueous Rechargeable Li and Na Ion Batteries Kim, Haegyeom; Hong, Jihyun; Park, Kyu-Young Chemical Reviews, Vol. 114, Issue 23 https://doi.org/10.1021/cr500232y	journal	September 2014
Site-Selective EXAFS in Mixed-Valence Compounds Using High-Resolution Fluorescence Detection: A Study of Iron in Prussian Blue Glatzel, Pieter; Jacquamet, Lilian; Bergmann, Uwe Inorganic Chemistry, Vol. 41, Issue 12 https://doi.org/10.1021/ic010709m	journal	June 2002
The crystal structure of Prussian Blue: Fe4[Fe(CN)6]3.xH2O Buser, H. J.; Schwarzenbach, D.; Petter, W. Inorganic Chemistry, Vol. 16, Issue 11, p. 2704-2710 https://doi.org/10.1021/ic50177a008	journal	November 1977
Polymorphism of Potassium Ferrocyanide Trihydrate as Studied by Solid-State Multinuclear NMR Spectroscopy and X-ray Diffraction Willans, Mathew J.; Wasylishen, Roderick E.; McDonald, Robert Inorganic Chemistry, Vol. 48, Issue 10 https://doi.org/10.1021/ic802134j	journal	April 2009
Fe L-Edge XAS Studies of K ₄ [Fe(CN) ₆ ] and K ₃ [Fe(CN) ₆ ]: A Direct Probe of Back-Bonding Hocking, Rosalie K.; Wasinger, Erik C.; de Groot, Frank M. F. Journal of the American Chemical Society, Vol. 128, Issue 32 https://doi.org/10.1021/ja061802i	journal	August 2006
A Multiplet Analysis of Fe K-Edge 1s → 3d Pre-Edge Features of Iron Complexes Westre, Tami E.; Kennepohl, Pierre; DeWitt, Jane G. Journal of the American Chemical Society, Vol. 119, Issue 27 https://doi.org/10.1021/ja964352a	journal	July 1997
Synchrotron Structural Characterization of Electrochemically Synthesized Hexacyanoferrates Containing K ⁺ : A Revisited Analysis of Electrochemical Redox Bueno, Paulo Roberto; Ferreira, Fabio Furlan; Giménez-Romero, David The Journal of Physical Chemistry C, Vol. 112, Issue 34 https://doi.org/10.1021/jp802070f	journal	August 2008
Nickel Hexacyanoferrate Nanoparticle Electrodes For Aqueous Sodium and Potassium Ion Batteries Wessells, Colin D.; Peddada, Sandeep V.; Huggins, Robert A. Nano Letters, Vol. 11, Issue 12, p. 5421-5425 https://doi.org/10.1021/nl203193q	journal	December 2011
Electroless Deposition of Conformal Nanoscale Iron Oxide on Carbon Nanoarchitectures for Electrochemical Charge Storage Sassin, Megan B.; Mansour, Azzam N.; Pettigrew, Katherine A. ACS Nano, Vol. 4, Issue 8 https://doi.org/10.1021/nn100572a	journal	July 2010
Structures and Formulæ of the Prussian Blues and Related Compounds Keggin, J. F.; Miles, F. D. Nature, Vol. 137, Issue 3466 https://doi.org/10.1038/137577a0	journal	April 1936
Invariant nature of substituted element in metal-hexacyanoferrate Niwa, Hideharu; Kobayashi, Wataru; Shibata, Takayuki Scientific Reports, Vol. 7, Issue 1 https://doi.org/10.1038/s41598-017-13719-z	journal	October 2017
Electrochemical capacitors: mechanism, materials, systems, characterization and applications Wang, Yonggang; Song, Yanfang; Xia, Yongyao Chemical Society Reviews, Vol. 45, Issue 21 https://doi.org/10.1039/C5CS00580A	journal	January 2016
Structural characterization of electrodeposited copper hexacyanoferrate films by using a spectroscopic multi-technique approach Giorgetti, Marco; Guadagnini, Lorella; Tonelli, Domenica Physical Chemistry Chemical Physics, Vol. 14, Issue 16 https://doi.org/10.1039/c2cp24109a	journal	January 2012
Crystal structures of the simple monoclinic and orthorhombic polytypes of tripotassium hexacyanoferrate(III) Figgis, Bn; Skelton, Bw; White, Ah Australian Journal of Chemistry, Vol. 31, Issue 6 https://doi.org/10.1071/CH9781195	journal	January 1978
EXAFS and XANES simulations of Fe/Co hexacyanoferrate spectra by GNXAS and MXAN Giorgetti, Marco; Longa, Stefano Della; Benfatto, Maurizio Journal of Physics: Conference Series, Vol. 190 https://doi.org/10.1088/1742-6596/190/1/012145	journal	November 2009
Structural and electronic studies of metal hexacyanoferrates based cathodes for Li rechargeable batteries Giorgetti, Marco; Mignani, Adriana; Aquilanti, Giuliana Journal of Physics: Conference Series, Vol. 712 https://doi.org/10.1088/1742-6596/712/1/012127	journal	May 2016
Thickness effect on the extended-x-ray-absorption-fine-structure amplitude Stern, E. A.; Kim, K. Physical Review B, Vol. 23, Issue 8 https://doi.org/10.1103/PhysRevB.23.3781	journal	April 1981
Multiple-scattering resonances and structural effects in the x-ray-absorption near-edge spectra of Fe II and Fe III hexacyanide complexes Bianconi, A.; Dell'Ariccia, M.; Durham, P. J. Physical Review B, Vol. 26, Issue 12 https://doi.org/10.1103/PhysRevB.26.6502	journal	December 1982
Characterization of magnetic CoFe cyanides by x-ray-absorption fine-structure spectroscopy Yokoyama, Toshihiko; Ohta, Toshiaki; Sato, Osamu Physical Review B, Vol. 58, Issue 13 https://doi.org/10.1103/PhysRevB.58.8257	journal	October 1998
X-ray transition energies: new approach to a comprehensive evaluation Deslattes, Richard D.; Kessler, Ernest G.; Indelicato, P. Reviews of Modern Physics, Vol. 75, Issue 1 https://doi.org/10.1103/RevModPhys.75.35	journal	January 2003
IFEFFIT : interactive XAFS analysis and FEFF fitting Newville, Matthew Journal of Synchrotron Radiation, Vol. 8, Issue 2 https://doi.org/10.1107/S0909049500016964	journal	March 2001
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT Ravel, B.; Newville, M. Journal of Synchrotron Radiation, Vol. 12, Issue 4 https://doi.org/10.1107/S0909049505012719	journal	June 2005
Nuclear Magnetic Resonance and X-Ray Studies of Potassium Ferrocyanide Trihydrate Crystal Kiriyama, Ryôiti; Kiriyama, Hideko; Wada, Takeo Journal of the Physical Society of Japan, Vol. 19, Issue 4 https://doi.org/10.1143/JPSJ.19.540	journal	April 1964
Crystal Structures of the Room- and Low-Temperature Phases of Monoclinic Potassium Ferricyanide Morioka, Yoshiyuki; Toriumi, Koshiro; Ito, Tasuku Journal of the Physical Society of Japan, Vol. 54, Issue 6 https://doi.org/10.1143/JPSJ.54.2184	journal	June 1985
Charge Transfer Effects on Fe 2 p X-ray Photoemission of RbMn[Fe(CN) ₆ ], K ₃ Fe(CN) ₆ , and K ₄ Fe(CN) ₆ Nanba, Yūsuke; Okada, Kozo Journal of the Physical Society of Japan, Vol. 80, Issue 7 https://doi.org/10.1143/JPSJ.80.074710	journal	July 2011
Experimental Studies of Mediator-Enhanced Polymer Electrolyte Supercapacitors Zhou, Juanjuan; Yin, Yijing; Mansour, Azzam N. Electrochemical and Solid-State Letters, Vol. 14, Issue 3 https://doi.org/10.1149/1.3526094	journal	January 2011
Electrochemical and In Situ Spectroscopic Study of the Effect of Prussian Blue as a Mediator in a Solid-State Supercapacitor qiao, xiaoyao; Yan, Zhiwei; zhang, chen Journal of The Electrochemical Society https://doi.org/10.1149/1945-7111/ac2ac6	journal	September 2021
A Review on the Structural Studies of Batteries and Host Materials by X-Ray Absorption Spectroscopy Giorgetti, Marco ISRN Materials Science, Vol. 2013 https://doi.org/10.1155/2013/938625	journal	January 2013
A Brief Review on Electrode Materials for Supercapacitor S. Iro, Zaharaddeen International Journal of Electrochemical Science https://doi.org/10.20964/2016.12.50	journal	December 2016

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