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

Journal Article · · Journal of Power Sources
 [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)
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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.

Research Organization:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC00112704; AC02-98CH10886
OSTI ID:
1340423
Alternate ID(s):
OSTI ID: 1341186
Report Number(s):
BNL-113337-2016-JA
Journal Information:
Journal of Power Sources, Vol. 321; ISSN 0378-7753
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 38 works
Citation information provided by
Web of Science

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Cited By (4)

Electrode Composite for Flexible Zinc–Manganese Dioxide Batteries through In Situ Polymerization of Polymer Hydrogel journal December 2019
Systematic cycle life assessment of a secondary zinc-air battery as a function of the alkaline electrolyte composition journal May 2018
An Operando Study of the Initial Discharge of Bi and Bi/Cu Modified MnO 2 journal January 2018
Recent Advances in Rational Electrode Designs for High-Performance Alkaline Rechargeable Batteries journal January 2019

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