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

The rechargeability of γ-MnO 2 cathodes in alkaline batteries is limited by the formation of the [Mn 2]O 4 spinels ZnMn 2O 4 (hetaerolite) and Mn 3O 4 (hausmannite). However, the time and formation mechanisms of these spinels are not well understood. Here we directly observe γ-MnO 2 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-MnO 2 the α-MnOOH phase forms rapidly. α-MnOOH is the precursor to spinel, which closely follows. ZnMn 2O 4 and Mn 3O 4 form at the same discharge depth, by the same mechanism. The results show the final discharge product, Mn 3O 4 or Mn(OH) 2, is not an intrinsic property of γ-MnO 2. While several studies have identified Mn(OH) 2 as the final γ-MnO 2 discharge product, we observe direct conversion to Mn 3O 4 withmore » no Mn(OH) 2.« less
Authors:
 [1] ;  [2] ;  [3] ;  [4] ;  [1] ;  [1] ;  [2] ;  [3] ;  [1]
  1. City College of New York, NY (United States)
  2. Princeton Univ., NJ (United States)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
  4. Rutgers Univ., Piscataway, NJ (United States)
Publication Date:
Report Number(s):
BNL-113337-2016-JA
Journal ID: ISSN 0378-7753
Grant/Contract Number:
SC00112704; AC02-98CH10886
Type:
Accepted Manuscript
Journal Name:
Journal of Power Sources
Additional Journal Information:
Journal Volume: 321; Journal ID: ISSN 0378-7753
Publisher:
Elsevier
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE
OSTI Identifier:
1340423
Alternate Identifier(s):
OSTI ID: 1341186

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., 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. 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., and Banerjee, Sanjoy. 2016. "Operando identification of the point of [Mn-2]O-4 spinel formation during gamma-MnO2 discharge within batteries". United States. doi: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 = {2016},
month = {5}
}