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Title: Deconvolution of Composition and Crystallite Size of Silver Hollandite Nanorods: Influence on Electrochemistry

Abstract

In this paper, silver hollandite (Ag1.4Mn8O16) has been synthesized by an aqueous, low-temperature co-precipitation technique to afford silver hollandite with distinct crystallite sizes (10 and 15 nm, identified as S-Ag1.4Mn8O16 and L-Ag1.4Mn8O16, respectively) and equivalent silver content (x), allowing for the deconvolution of electrochemical effects related to crystallite size and silver content. The as-prepared silver hollandite materials were confirmed to be structurally analogous. Notably, TEM imaging reveals a high degree of bundling of S-Ag1.4Mn8O16 nanorods compared to L-Ag1.4Mn8O16 which facilitates more intimate connection of the S-Ag1.4Mn8O16 material with enhanced interparticle contact. The electrochemical behavior and lithium diffusion properties were investigated by galvanostatic cycling, CV, electrochemical impedance, pulsed-discharge experiments, and ex-situ XAS analysis of cycled cathodes. Lithium based electrochemical cells containing S-Ag1.4Mn8O16 delivered a capacity 15X higher than L-Ag1.4Mn8O16 on cycle 1. Ex-situ XAS demonstrated structural change for S-Ag1.4Mn8O16 and formation of Ag0 on insertion of 3.8 Li+ intercalation. However, the samples of L-Ag1.4Mn8O16 were lithiated by a more limited 0.25 molar equivalents, where no significant structural changes were observed. Finally, the findings affirm crystallite size significantly impacts electrochemistry independent of cation occupancy of the α-MnO2 type structure.

Authors:
 [1]; ORCiD logo [1];  [1];  [2];  [2];  [2];  [2];  [3];  [4];  [4]
  1. Stony Brook Univ., NY (United States). Dept. of Chemistry
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). Energy Sciences Directorate
  3. Stony Brook Univ., NY (United States). Dept. of Chemistry. Dept. of Materials Science and Chemical Engineering; Brookhaven National Lab. (BNL), Upton, NY (United States). Energy Sciences Directorate
  4. Stony Brook Univ., NY (United States). Dept. of Chemistry. Dept. of Materials Science and Chemical Engineering
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., NY (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2M)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1425104
Report Number(s):
BNL-203324-2018-JAAM
Journal ID: ISSN 0013-4651
Grant/Contract Number:  
SC0012704; SC0012673; AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 164; Journal Issue: 14; Journal ID: ISSN 0013-4651
Publisher:
The Electrochemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Durham, Jessica L., Huang, Jianping, Zhang, Bingjie, Wu, Lijun, Tong, Xiao, Pelliccione, Christopher J., Zhu, Yimei, Takeuchi, Esther S., Marschilok, Amy C., and Takeuchi, Kenneth J. Deconvolution of Composition and Crystallite Size of Silver Hollandite Nanorods: Influence on Electrochemistry. United States: N. p., 2017. Web. doi:10.1149/2.1371714jes.
Durham, Jessica L., Huang, Jianping, Zhang, Bingjie, Wu, Lijun, Tong, Xiao, Pelliccione, Christopher J., Zhu, Yimei, Takeuchi, Esther S., Marschilok, Amy C., & Takeuchi, Kenneth J. Deconvolution of Composition and Crystallite Size of Silver Hollandite Nanorods: Influence on Electrochemistry. United States. https://doi.org/10.1149/2.1371714jes
Durham, Jessica L., Huang, Jianping, Zhang, Bingjie, Wu, Lijun, Tong, Xiao, Pelliccione, Christopher J., Zhu, Yimei, Takeuchi, Esther S., Marschilok, Amy C., and Takeuchi, Kenneth J. 2017. "Deconvolution of Composition and Crystallite Size of Silver Hollandite Nanorods: Influence on Electrochemistry". United States. https://doi.org/10.1149/2.1371714jes. https://www.osti.gov/servlets/purl/1425104.
@article{osti_1425104,
title = {Deconvolution of Composition and Crystallite Size of Silver Hollandite Nanorods: Influence on Electrochemistry},
author = {Durham, Jessica L. and Huang, Jianping and Zhang, Bingjie and Wu, Lijun and Tong, Xiao and Pelliccione, Christopher J. and Zhu, Yimei and Takeuchi, Esther S. and Marschilok, Amy C. and Takeuchi, Kenneth J.},
abstractNote = {In this paper, silver hollandite (Ag1.4Mn8O16) has been synthesized by an aqueous, low-temperature co-precipitation technique to afford silver hollandite with distinct crystallite sizes (10 and 15 nm, identified as S-Ag1.4Mn8O16 and L-Ag1.4Mn8O16, respectively) and equivalent silver content (x), allowing for the deconvolution of electrochemical effects related to crystallite size and silver content. The as-prepared silver hollandite materials were confirmed to be structurally analogous. Notably, TEM imaging reveals a high degree of bundling of S-Ag1.4Mn8O16 nanorods compared to L-Ag1.4Mn8O16 which facilitates more intimate connection of the S-Ag1.4Mn8O16 material with enhanced interparticle contact. The electrochemical behavior and lithium diffusion properties were investigated by galvanostatic cycling, CV, electrochemical impedance, pulsed-discharge experiments, and ex-situ XAS analysis of cycled cathodes. Lithium based electrochemical cells containing S-Ag1.4Mn8O16 delivered a capacity 15X higher than L-Ag1.4Mn8O16 on cycle 1. Ex-situ XAS demonstrated structural change for S-Ag1.4Mn8O16 and formation of Ag0 on insertion of 3.8 Li+ intercalation. However, the samples of L-Ag1.4Mn8O16 were lithiated by a more limited 0.25 molar equivalents, where no significant structural changes were observed. Finally, the findings affirm crystallite size significantly impacts electrochemistry independent of cation occupancy of the α-MnO2 type structure.},
doi = {10.1149/2.1371714jes},
url = {https://www.osti.gov/biblio/1425104}, journal = {Journal of the Electrochemical Society},
issn = {0013-4651},
number = 14,
volume = 164,
place = {United States},
year = {Sat Dec 16 00:00:00 EST 2017},
month = {Sat Dec 16 00:00:00 EST 2017}
}

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Works referencing / citing this record:

Review of the Stability/Capacity Trade-off in Silver Hollandite Lithium Battery Cathodes
journal, January 2018