Operando identification of the point of [Mn-2]O-4 spinel formation during gamma-MnO2 discharge within batteries
Abstract
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.
- Authors:
-
- 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)
- Publication Date:
- Research Org.:
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1340423
- Alternate Identifier(s):
- OSTI ID: 1341186
- Report Number(s):
- BNL-113337-2016-JA
Journal ID: ISSN 0378-7753
- Grant/Contract Number:
- SC00112704; AC02-98CH10886
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Power Sources
- Additional Journal Information:
- Journal Volume: 321; Journal ID: ISSN 0378-7753
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE
Citation Formats
Gallaway, Joshua W., Hertzberg, Benjamin J., Zhong, Zhong, Croft, Mark, Turney, Damon E., Yadav, Gautam G., Steingart, Daniel A., Erdonmez, Can K., and Banerjee, Sanjoy. Operando identification of the point of [Mn-2]O-4 spinel formation during gamma-MnO2 discharge within batteries. United States: N. p., 2016.
Web. doi:10.1016/j.jpowsour.2016.05.002.
Gallaway, Joshua W., Hertzberg, Benjamin J., Zhong, Zhong, Croft, Mark, Turney, Damon E., Yadav, Gautam G., Steingart, Daniel A., Erdonmez, Can K., & Banerjee, Sanjoy. Operando identification of the point of [Mn-2]O-4 spinel formation during gamma-MnO2 discharge within batteries. United States. https://doi.org/10.1016/j.jpowsour.2016.05.002
Gallaway, Joshua W., Hertzberg, Benjamin J., Zhong, Zhong, Croft, Mark, Turney, Damon E., Yadav, Gautam G., Steingart, Daniel A., Erdonmez, Can K., and Banerjee, Sanjoy. Sat .
"Operando identification of the point of [Mn-2]O-4 spinel formation during gamma-MnO2 discharge within batteries". United States. https://doi.org/10.1016/j.jpowsour.2016.05.002. https://www.osti.gov/servlets/purl/1340423.
@article{osti_1340423,
title = {Operando identification of the point of [Mn-2]O-4 spinel formation during gamma-MnO2 discharge within batteries},
author = {Gallaway, Joshua W. and Hertzberg, Benjamin J. and Zhong, Zhong and Croft, Mark and Turney, Damon E. and Yadav, Gautam G. and Steingart, Daniel A. and Erdonmez, Can K. and Banerjee, Sanjoy},
abstractNote = {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.},
doi = {10.1016/j.jpowsour.2016.05.002},
journal = {Journal of Power Sources},
number = ,
volume = 321,
place = {United States},
year = {Sat May 07 00:00:00 EDT 2016},
month = {Sat May 07 00:00:00 EDT 2016}
}
Web of Science
Works referenced in this record:
The Manganese Dioxide Electrode in Alkaline Electrolyte; The Electron-Proton Mechanism for the Discharge Process from MnO[sub 2] to MnO[sub 1.5]
journal, January 1966
- Kozawa, A.; Powers, R. A.
- Journal of The Electrochemical Society, Vol. 113, Issue 9
Cathodic Polarization of the Manganese Dioxide Electrode in Alkaline Electrolytes
journal, January 1968
- Kozawa, A.; Powers, R. A.
- Journal of The Electrochemical Society, Vol. 115, Issue 2
The Alkaline Manganese Dioxide Electrode
journal, January 1967
- Boden, David; Venuto, C. J.; Wisler, D.
- Journal of The Electrochemical Society, Vol. 114, Issue 5
The electrochemistry of β-MnO2 and γ-MnO2 in alkaline electrolyte
journal, March 1975
- McBreen, James
- Electrochimica Acta, Vol. 20, Issue 3
Rechargeable Alkaline Manganese Dioxide Batteries
journal, January 1992
- Mondoloni, Christian
- Journal of The Electrochemical Society, Vol. 139, Issue 4
Understanding the Second Electron Discharge Plateau in MnO[sub 2]-Based Alkaline Cells
journal, January 2001
- Patrice, R.; Gérand, B.; Leriche, J. B.
- Journal of The Electrochemical Society, Vol. 148, Issue 5
[sup 2]H MAS NMR and SPECS Studies of γ-MnO[sub 2] Reduction in Zinc Alkaline Primary Batteries
journal, January 2004
- Paik, Younkee; Bowden, William; Richards, Thomas
- Journal of The Electrochemical Society, Vol. 151, Issue 7
In situ visualization of Li/Ag2VP2O8 batteries revealing rate-dependent discharge mechanism
journal, January 2015
- Kirshenbaum, K.; Bock, D. C.; Lee, C. -Y.
- Science, Vol. 347, Issue 6218
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
journal, January 2015
- Kirshenbaum, Kevin C.; Bock, David C.; Zhong, Zhong
- Journal of Materials Chemistry A, Vol. 3, Issue 35
In situ X-ray diffraction of prototype sodium metal halide cells: Time and space electrochemical profiling
journal, February 2011
- Rijssenbeek, Job; Gao, Yan; Zhong, Zhong
- Journal of Power Sources, Vol. 196, Issue 4
Hetaerolite Profiles in Alkaline Batteries Measured by High Energy EDXRD
journal, November 2014
- Gallaway, Joshua W.; Menard, Melissa; Hertzberg, Benjamin
- Journal of The Electrochemical Society, Vol. 162, Issue 1
Rechargeability and economic aspects of alkaline zinc–manganese dioxide cells for electrical storage and load leveling
journal, February 2015
- Ingale, Nilesh D.; Gallaway, Joshua W.; Nyce, Michael
- Journal of Power Sources, Vol. 276
In situ strain profiling of elastoplastic bending in Ti–6Al–4V alloy by synchrotron energy dispersive x-ray diffraction
journal, May 2009
- Croft, M.; Shukla, V.; Akdoğan, E. K.
- Journal of Applied Physics, Vol. 105, Issue 9
Strain field and scattered intensity profiling with energy dispersive x-ray scattering
journal, July 2002
- Croft, M.; Zakharchenko, I.; Zhong, Z.
- Journal of Applied Physics, Vol. 92, Issue 1
Modeling of Cylindrical Alkaline Cells
journal, January 1993
- Chen, Jenn-Shing
- Journal of The Electrochemical Society, Vol. 140, Issue 5
Porous-electrode theory with battery applications
journal, January 1975
- Newman, John; Tiedemann, William
- AIChE Journal, Vol. 21, Issue 1
Mathematical Modeling of the Lithium‐Aluminum, Iron Sulfide Battery: II . The Influence of Relaxation Time on the Charging Characteristics
journal, March 1981
- Pollard, Richard; Newman, John
- Journal of The Electrochemical Society, Vol. 128, Issue 3
Structural and electrochemical properties of the proton / γ-MnO2 system
journal, January 1995
- Chabre, Y.; Pannetier, J.
- Progress in Solid State Chemistry, Vol. 23, Issue 1
Structural effects on the cyclability of the alkaline γ-MnO2 electrode
journal, May 2011
- Bailey, Mark R.; Donne, Scott W.
- Electrochimica Acta, Vol. 56, Issue 14
The Cathodic Reduction Mechanism of Electrolytic Manganese Dioxide in Alkaline Electrolyte
journal, January 1965
- Kozawa, A.; Yeager, J. F.
- Journal of The Electrochemical Society, Vol. 112, Issue 10
Hydrogen Bonding and Jahn–Teller Distortion in Groutite,α-MnOOH, and Manganite,γ-MnOOH, and Their Relations to the Manganese Dioxides Ramsdellite and Pyrolusite
journal, November 1997
- Kohler, Thomas; Armbruster, Thomas; Libowitzky, Eugen
- Journal of Solid State Chemistry, Vol. 133, Issue 2
The Structure of Fully H-Inserted γ-Manganese Dioxide Compounds
journal, April 1996
- MacLean, L. A. H.; Tye, F. L.
- Journal of Solid State Chemistry, Vol. 123, Issue 1
Manganese Dioxides: Structural Model and In-Situ Neutron Powder Diffraction Investigation of Thermal Annealing and Electrochemical Reduction
journal, January 1990
- Ripert, M.; Pannetier, J.; Chabre, Y.
- MRS Proceedings, Vol. 210
Structural study of proton electrochemical intercalation in manganese dioxide
journal, April 1991
- Ripert, M.; Poinsignon, C.; Chabre, Y.
- Phase Transitions, Vol. 32, Issue 1-4
2 H MAS NMR Studies of the Manganese Dioxide Tunnel Structures and Hydroxides Used as Cathode Materials in Primary Batteries
journal, September 2001
- Paik, Younkee; Osegovic, John P.; Wang, Francis
- Journal of the American Chemical Society, Vol. 123, Issue 38
Rechargeability of MnO[sub 2] in KOH Media Produced by Decomposition of Dissolved KMnO[sub 4] and Bi(NO[sub 3])[sub 3] Mixtures
journal, January 1997
- Yu, L. T.
- Journal of The Electrochemical Society, Vol. 144, Issue 3
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
journal, January 2003
- Im, D.; Manthiram, A.; Coffey, B.
- Journal of The Electrochemical Society, Vol. 150, Issue 12
Ramsdellite-MnO2 for lithium batteries: the ramsdellite to spinel transformation
journal, June 1993
- Thackeray, M. M.; Rossouw, M. H.; Gummow, R. J.
- Electrochimica Acta, Vol. 38, Issue 9
Lithium insertion into βMnO2 and the rutile-spinel transformation
journal, January 1984
- David, W. I. F.; Thackeray, M. M.; Bruce, P. G.
- Materials Research Bulletin, Vol. 19, Issue 1
Works referencing / citing this record:
Electrode Composite for Flexible Zinc–Manganese Dioxide Batteries through In Situ Polymerization of Polymer Hydrogel
journal, December 2019
- Zamarayeva, Alla M.; Jegraj, Akshaya; Toor, Anju
- Energy Technology, Vol. 8, Issue 3
Systematic cycle life assessment of a secondary zinc-air battery as a function of the alkaline electrolyte composition
journal, May 2018
- Mainar, Aroa R.; Iruin, Elena; Colmenares, Luis C.
- Energy Science & Engineering, Vol. 6, Issue 3
An Operando Study of the Initial Discharge of Bi and Bi/Cu Modified MnO 2
journal, January 2018
- Gallaway, Joshua W.; Yadav, Gautam G.; Turney, Damon E.
- Journal of The Electrochemical Society, Vol. 165, Issue 13
Recent Advances in Rational Electrode Designs for High-Performance Alkaline Rechargeable Batteries
journal, January 2019
- Huang, Meng; Li, Ming; Niu, Chaojiang
- Advanced Functional Materials, Vol. 29, Issue 11