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Title: An Operando Study of the Initial Discharge of Bi and Bi/Cu Modified MnO 2

Abstract

It was recently reported that inclusion of Cu in Bi-modified MnO 2 cathodes allowed over 1000 cycles at nearly the full capacity of 617 mAh/g-MnO 2, at a high areal capacity of 28 mAh/cm 2. To better understand the molecular mechanism by which Bi and Cu impart rechargeability, cathodes prepared by physical mixing of MnO 2 and Bi 2O 3 were studied during initial discharge at an areal capacity of 57.4 mAh/cm 2, both with Cu (MDBC) and without (MDB). These were compared to the base case with MnO 2 only (MD). It is demonstrated that there are two distinct regimes of Mn II production during the second electron regime of discharge. In standard MD cathodes, the first regime results in an amorphous product formed simultaneously with Mn 3O 4, while the second results in crystalline Mn(OH) 2. When MnO 2 is Bi-modified, crystalline Mn(OH) 2 is formed in both regimes and Mn 3O 4 is absent. Bi and Cu are observed to have a structural effect on the α-MnOOH discharge intermediate. Cu II is shown to be electrochemically active at the surfaces of MnO 2 particles, reducing to Cu I and Cu 0. Reversible potentials suggest Mn II wouldmore » act as a redox mediator, reducing Cu II. In conclusion, fluorescence mapping provides evidence for occurrence of this phenomenon.« less

Authors:
ORCiD logo [1];  [2];  [2];  [2];  [2];  [3];  [4];  [4];  [5]; ORCiD logo [2];  [2]
  1. Northeastern Univ., Boston, MA (United States)
  2. The City College of New York, New York, NY (United States)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., Stony Brook, NY (United States)
  4. Brookhaven National Lab. (BNL), Upton, NY (United States)
  5. Argonne National Lab. (ANL), Lemont, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Advanced Research Projects Agency - Energy (ARPA-E)
OSTI Identifier:
1471126
Alternate Identifier(s):
OSTI ID: 1477743; OSTI ID: 1480921
Report Number(s):
BNL-209419-2018-JAAM
Journal ID: ISSN 0013-4651; 146434
Grant/Contract Number:  
AC02-06CH11357; AR0000150; SC0012704
Resource Type:
Published Article
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 165; Journal Issue: 13; Journal ID: ISSN 0013-4651
Publisher:
The Electrochemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; alkaline battery; manganese dioxide; operando; 36 MATERIALS SCIENCE

Citation Formats

Gallaway, Joshua W., Yadav, Gautam G., Turney, Damon E., Nyce, Michael, Huang, Jinchao, Chen-Wiegart, Yu-chen Karen, Williams, Garth, Thieme, Juergen, Okasinski, John S., Wei, Xia, and Banerjee, Sanjoy. An Operando Study of the Initial Discharge of Bi and Bi/Cu Modified MnO2. United States: N. p., 2018. Web. doi:10.1149/2.0221813jes.
Gallaway, Joshua W., Yadav, Gautam G., Turney, Damon E., Nyce, Michael, Huang, Jinchao, Chen-Wiegart, Yu-chen Karen, Williams, Garth, Thieme, Juergen, Okasinski, John S., Wei, Xia, & Banerjee, Sanjoy. An Operando Study of the Initial Discharge of Bi and Bi/Cu Modified MnO2. United States. doi:10.1149/2.0221813jes.
Gallaway, Joshua W., Yadav, Gautam G., Turney, Damon E., Nyce, Michael, Huang, Jinchao, Chen-Wiegart, Yu-chen Karen, Williams, Garth, Thieme, Juergen, Okasinski, John S., Wei, Xia, and Banerjee, Sanjoy. Sat . "An Operando Study of the Initial Discharge of Bi and Bi/Cu Modified MnO2". United States. doi:10.1149/2.0221813jes.
@article{osti_1471126,
title = {An Operando Study of the Initial Discharge of Bi and Bi/Cu Modified MnO2},
author = {Gallaway, Joshua W. and Yadav, Gautam G. and Turney, Damon E. and Nyce, Michael and Huang, Jinchao and Chen-Wiegart, Yu-chen Karen and Williams, Garth and Thieme, Juergen and Okasinski, John S. and Wei, Xia and Banerjee, Sanjoy},
abstractNote = {It was recently reported that inclusion of Cu in Bi-modified MnO2 cathodes allowed over 1000 cycles at nearly the full capacity of 617 mAh/g-MnO2, at a high areal capacity of 28 mAh/cm2. To better understand the molecular mechanism by which Bi and Cu impart rechargeability, cathodes prepared by physical mixing of MnO2 and Bi2O3 were studied during initial discharge at an areal capacity of 57.4 mAh/cm2, both with Cu (MDBC) and without (MDB). These were compared to the base case with MnO2 only (MD). It is demonstrated that there are two distinct regimes of MnII production during the second electron regime of discharge. In standard MD cathodes, the first regime results in an amorphous product formed simultaneously with Mn3O4, while the second results in crystalline Mn(OH)2. When MnO2 is Bi-modified, crystalline Mn(OH)2 is formed in both regimes and Mn3O4 is absent. Bi and Cu are observed to have a structural effect on the α-MnOOH discharge intermediate. CuII is shown to be electrochemically active at the surfaces of MnO2 particles, reducing to CuI and Cu0. Reversible potentials suggest MnII would act as a redox mediator, reducing CuII. In conclusion, fluorescence mapping provides evidence for occurrence of this phenomenon.},
doi = {10.1149/2.0221813jes},
journal = {Journal of the Electrochemical Society},
number = 13,
volume = 165,
place = {United States},
year = {2018},
month = {9}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1149/2.0221813jes

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