Operando identification of the point of [Mn-2]O-4 spinel formation during gamma-MnO2 discharge within batteries

Gallaway, Joshua W.; Hertzberg, Benjamin J.; Zhong, Zhong; Croft, Mark; Turney, Damon E.; Yadav, Gautam G.; Steingart, Daniel A.; Erdonmez, Can K.; Banerjee, Sanjoy

doi:10.1016/j.jpowsour.2016.05.002

Operando identification of the point of [Mn-₂]O-₄ spinel formation during gamma-MnO₂ discharge within batteries

Journal Article · Sat May 07 00:00:00 EDT 2016 · Journal of Power Sources

DOI:https://doi.org/10.1016/j.jpowsour.2016.05.002· OSTI ID:1340423

Gallaway, Joshua W. ^[1]; Hertzberg, Benjamin J. ^[2]; Zhong, Zhong ^[3]; Croft, Mark ^[4]; Turney, Damon E. ^[1]; Yadav, Gautam G. ^[1]; Steingart, Daniel A. ^[2]; Erdonmez, Can K. ^[3]; Banerjee, Sanjoy ^[1]

City College of New York, NY (United States)
Princeton Univ., NJ (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Rutgers Univ., Piscataway, NJ (United States)

The rechargeability of γ-MnO₂ cathodes in alkaline batteries is limited by the formation of the [Mn₂]O₄ spinels ZnMn₂O₄ (hetaerolite) and Mn₃O₄ (hausmannite). However, the time and formation mechanisms of these spinels are not well understood. Here we directly observe γ-MnO₂ discharge at a range of reaction extents distributed across a thick porous electrode. Coupled with a battery model, this reveals that spinel formation occurs at a precise and predictable point in the reaction, regardless of reaction rate. Observation is accomplished by energy dispersive X-ray diffraction (EDXRD) using photons of high energy and high flux, which penetrate the cell and provide diffraction data as a function of location and time. After insertion of 0.79 protons per γ-MnO₂ the α-MnOOH phase forms rapidly. α-MnOOH is the precursor to spinel, which closely follows. ZnMn₂O₄ and Mn₃O₄ form at the same discharge depth, by the same mechanism. The results show the final discharge product, Mn₃O₄ or Mn(OH)₂, is not an intrinsic property of γ-MnO₂. While several studies have identified Mn(OH)₂ as the final γ-MnO₂ discharge product, we observe direct conversion to Mn₃O₄ with no Mn(OH)₂.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

OSTI ID:: 1340423

Alternate ID(s):: OSTI ID: 1341186
OSTI ID: 1354463

Report Number(s):: BNL--113337-2016-JA

Journal Information:: Journal of Power Sources, Journal Name: Journal of Power Sources Vol. 321; ISSN 0378-7753

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (30)

Porous-electrode theory with battery applications Newman, John; Tiedemann, William AIChE Journal, Vol. 21, Issue 1 https://doi.org/10.1002/aic.690210103	journal	January 1975
The Structure of Fully H-Inserted γ-Manganese Dioxide Compounds MacLean, L. A. H.; Tye, F. L. Journal of Solid State Chemistry, Vol. 123, Issue 1 https://doi.org/10.1006/jssc.1996.0163	journal	April 1996
Hydrogen Bonding and Jahn–Teller Distortion in Groutite,α-MnOOH, and Manganite,γ-MnOOH, and Their Relations to the Manganese Dioxides Ramsdellite and Pyrolusite Kohler, Thomas; Armbruster, Thomas; Libowitzky, Eugen Journal of Solid State Chemistry, Vol. 133, Issue 2 https://doi.org/10.1006/jssc.1997.7516	journal	November 1997
The electrochemistry of β-MnO2 and γ-MnO2 in alkaline electrolyte McBreen, James Electrochimica Acta, Vol. 20, Issue 3 https://doi.org/10.1016/0013-4686(75)85028-6	journal	March 1975
Ramsdellite-MnO2 for lithium batteries: the ramsdellite to spinel transformation Thackeray, M. M.; Rossouw, M. H.; Gummow, R. J. Electrochimica Acta, Vol. 38, Issue 9 https://doi.org/10.1016/0013-4686(93)80056-6	journal	June 1993
Lithium insertion into βMnO2 and the rutile-spinel transformation David, W. I. F.; Thackeray, M. M.; Bruce, P. G. Materials Research Bulletin, Vol. 19, Issue 1 https://doi.org/10.1016/0025-5408(84)90015-1	journal	January 1984
Structural and electrochemical properties of the proton / γ-MnO2 system Chabre, Y.; Pannetier, J. Progress in Solid State Chemistry, Vol. 23, Issue 1 https://doi.org/10.1016/0079-6786(94)00005-2	journal	January 1995
Structural effects on the cyclability of the alkaline γ-MnO2 electrode Bailey, Mark R.; Donne, Scott W. Electrochimica Acta, Vol. 56, Issue 14 https://doi.org/10.1016/j.electacta.2011.03.095	journal	May 2011
In situ X-ray diffraction of prototype sodium metal halide cells: Time and space electrochemical profiling Rijssenbeek, Job; Gao, Yan; Zhong, Zhong Journal of Power Sources, Vol. 196, Issue 4 https://doi.org/10.1016/j.jpowsour.2010.10.023	journal	February 2011
Rechargeability and economic aspects of alkaline zinc–manganese dioxide cells for electrical storage and load leveling Ingale, Nilesh D.; Gallaway, Joshua W.; Nyce, Michael Journal of Power Sources, Vol. 276 https://doi.org/10.1016/j.jpowsour.2014.11.010	journal	February 2015
² H MAS NMR Studies of the Manganese Dioxide Tunnel Structures and Hydroxides Used as Cathode Materials in Primary Batteries Paik, Younkee; Osegovic, John P.; Wang, Francis Journal of the American Chemical Society, Vol. 123, Issue 38 https://doi.org/10.1021/ja015999k	journal	September 2001
Real-time materials evolution visualized within intact cycling alkaline batteries Gallaway, Joshua W.; Erdonmez, Can K.; Zhong, Zhong J. Mater. Chem. A, Vol. 2, Issue 8 https://doi.org/10.1039/C3TA15169G	journal	January 2014
Electrochemical reduction of Ag ₂ VP ₂ O ₈ composite electrodes visualized via in situ energy dispersive X-ray diffraction (EDXRD): unexpected conductive additive effects Kirshenbaum, Kevin C.; Bock, David C.; Zhong, Zhong Journal of Materials Chemistry A, Vol. 3, Issue 35 https://doi.org/10.1039/C5TA04523A	journal	January 2015
Strain field and scattered intensity profiling with energy dispersive x-ray scattering Croft, M.; Zakharchenko, I.; Zhong, Z. Journal of Applied Physics, Vol. 92, Issue 1 https://doi.org/10.1063/1.1483373	journal	July 2002
In situ strain profiling of elastoplastic bending in Ti–6Al–4V alloy by synchrotron energy dispersive x-ray diffraction Croft, M.; Shukla, V.; Akdoğan, E. K. Journal of Applied Physics, Vol. 105, Issue 9 https://doi.org/10.1063/1.3122029	journal	May 2009
Structural study of proton electrochemical intercalation in manganese dioxide Ripert, M.; Poinsignon, C.; Chabre, Y. Phase Transitions, Vol. 32, Issue 1-4 https://doi.org/10.1080/01411599108219177	journal	April 1991
In situ visualization of Li/Ag2VP2O8 batteries revealing rate-dependent discharge mechanism Kirshenbaum, K.; Bock, D. C.; Lee, C. -Y. Science, Vol. 347, Issue 6218 https://doi.org/10.1126/science.1257289	journal	January 2015
Understanding the Second Electron Discharge Plateau in MnO[sub 2]-Based Alkaline Cells Patrice, R.; Gérand, B.; Leriche, J. B. Journal of The Electrochemical Society, Vol. 148, Issue 5 https://doi.org/10.1149/1.1362539	journal	January 2001
Manganese(III) Chemistry in KOH Solutions in the Presence of Bi- or Ba-Containing Compounds and Its Implications on the Rechargeability of γ-MnO[sub 2] in Alkaline Cells Im, D.; Manthiram, A.; Coffey, B. Journal of The Electrochemical Society, Vol. 150, Issue 12 https://doi.org/10.1149/1.1622960	journal	January 2003
[sup 2]H MAS NMR and SPECS Studies of γ-MnO[sub 2] Reduction in Zinc Alkaline Primary Batteries Paik, Younkee; Bowden, William; Richards, Thomas Journal of The Electrochemical Society, Vol. 151, Issue 7 https://doi.org/10.1149/1.1757459	journal	January 2004
Rechargeability of MnO[sub 2] in KOH Media Produced by Decomposition of Dissolved KMnO[sub 4] and Bi(NO[sub 3])[sub 3] Mixtures Yu, L. T. Journal of The Electrochemical Society, Vol. 144, Issue 3 https://doi.org/10.1149/1.1837492	journal	January 1997
Rechargeable Alkaline Manganese Dioxide Batteries Mondoloni, Christian Journal of The Electrochemical Society, Vol. 139, Issue 4 https://doi.org/10.1149/1.2069374	journal	January 1992
Mathematical Modeling of the Lithium‐Aluminum, Iron Sulfide Battery: II . The Influence of Relaxation Time on the Charging Characteristics Pollard, Richard; Newman, John Journal of The Electrochemical Society, Vol. 128, Issue 3 https://doi.org/10.1149/1.2127446	journal	March 1981
Modeling of Cylindrical Alkaline Cells Chen, Jenn-Shing Journal of The Electrochemical Society, Vol. 140, Issue 5 https://doi.org/10.1149/1.2220958	journal	January 1993
Cathodic Polarization of the Manganese Dioxide Electrode in Alkaline Electrolytes Kozawa, A.; Powers, R. A. Journal of The Electrochemical Society, Vol. 115, Issue 2 https://doi.org/10.1149/1.2411042	journal	January 1968
The Cathodic Reduction Mechanism of Electrolytic Manganese Dioxide in Alkaline Electrolyte Kozawa, A.; Yeager, J. F. Journal of The Electrochemical Society, Vol. 112, Issue 10 https://doi.org/10.1149/1.2423350	journal	January 1965
The Manganese Dioxide Electrode in Alkaline Electrolyte; The Electron-Proton Mechanism for the Discharge Process from MnO[sub 2] to MnO[sub 1.5] Kozawa, A.; Powers, R. A. Journal of The Electrochemical Society, Vol. 113, Issue 9 https://doi.org/10.1149/1.2424145	journal	January 1966
The Alkaline Manganese Dioxide Electrode Boden, David; Venuto, C. J.; Wisler, D. Journal of The Electrochemical Society, Vol. 114, Issue 5 https://doi.org/10.1149/1.2426618	journal	January 1967
Hetaerolite Profiles in Alkaline Batteries Measured by High Energy EDXRD Gallaway, Joshua W.; Menard, Melissa; Hertzberg, Benjamin Journal of The Electrochemical Society, Vol. 162, Issue 1 https://doi.org/10.1149/2.0811501jes	journal	November 2014
Manganese Dioxides: Structural Model and In-Situ Neutron Powder Diffraction Investigation of Thermal Annealing and Electrochemical Reduction Ripert, M.; Pannetier, J.; Chabre, Y. MRS Proceedings, Vol. 210 https://doi.org/10.1557/PROC-210-359	journal	January 1990

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Electrode Composite for Flexible Zinc–Manganese Dioxide Batteries through In Situ Polymerization of Polymer Hydrogel Zamarayeva, Alla M.; Jegraj, Akshaya; Toor, Anju Energy Technology, Vol. 8, Issue 3 https://doi.org/10.1002/ente.201901165	journal	December 2019
Systematic cycle life assessment of a secondary zinc-air battery as a function of the alkaline electrolyte composition Mainar, Aroa R.; Iruin, Elena; Colmenares, Luis C. Energy Science & Engineering, Vol. 6, Issue 3 https://doi.org/10.1002/ese3.191	journal	May 2018
An Operando Study of the Initial Discharge of Bi and Bi/Cu Modified MnO ₂ Gallaway, Joshua W.; Yadav, Gautam G.; Turney, Damon E. Journal of The Electrochemical Society, Vol. 165, Issue 13 https://doi.org/10.1149/2.0221813jes	journal	January 2018

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