Capacity Retention for (De)lithiation of Silver Containing α-MnO2 : Impact of Structural Distortion and Transition Metal Dissolution

Huang, Jianping; Housel, Lisa M.; Quilty, Calvin D.; Brady, Alexander B.; Smith, Paul F.; Abraham, Alyson; Dunkin, Mikaela R.; Lutz, Diana M.; Zhang, Bingjie; Takeuchi, Esther S.; Marschilok, Amy C.; Takeuchi, Kenneth J.

doi:10.1149/2.0371811jes

Title: Capacity Retention for (De)lithiation of Silver Containing α-MnO₂ : Impact of Structural Distortion and Transition Metal Dissolution

Journal Article · Wed Sep 05 00:00:00 EDT 2018 · Journal of the Electrochemical Society

DOI:https://doi.org/10.1149/2.0371811jes· OSTI ID:1475147

^[1]; Housel, Lisa M. ^[1]; Quilty, Calvin D. ^[1]; Brady, Alexander B. ^[2]; Smith, Paul F. ^[1]; Abraham, Alyson ^[1]; Dunkin, Mikaela R. ^[2];

^[1]; Zhang, Bingjie ^[1];

^[3];

^[4]

Stony Brook Univ., NY (United States). Dept. of Chemistry
Stony Brook Univ., NY (United States). Dept. of Materials Science and Chemical Engineering
Stony Brook Univ., NY (United States). Dept. of Chemistry; Stony Brook Univ., NY (United States). Dept. of Materials Science and Chemical Engineering; Brookhaven National Lab. (BNL), Upton, NY (United States). Energy Sciences Directorate
Stony Brook Univ., NY (United States). Dept. of Chemistry; Stony Brook Univ., NY (United States). Dept. of Materials Science and Chemical Engineering

Crystallite size reduction is a strategy utilized to increase deliverable capacity by decreasing the path length for lithium ion diffusion. However, reduction in crystallite size may also exacerbate unfavorable reactions within a battery limiting cycle life. Here, differences in capacity retention are observed for silver containing α-MnO₂ (silver hollandite, AgHol), with two crystallite sizes. Under 30 mA/g discharge, the smaller crystallite size material (AgHol-S, 7 nm) delivers 266 mAh/g initial capacity with 91% capacity decrease from cycles 2 - 50. In contrast, the larger crystallite size material (AgHol-L, 80 nm) has an initial capacity of 129 mAh/g and only 9% decrease from cycles 2 - 50. A second electrochemical test was conducted using a capacity limit rather than a voltage limit. Under those test conditions, the structural distortion for the two materials observed by X-ray Absorption Spectroscopy (XAS) was similar, yet the terminal voltage decrease was more significant for the small crystallite sized sample. Determination of Mn dissolution revealed Mn solubility 5.4X higher for AgHol-S than AgHol-L with accompanying higher Mn deposition on the negative electrode and increased cell impedance. In conclusion, this study provides quantitative determination of capacity fade as related to structural distortion and transition metal dissolution as related to crystallite size.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2mt); Brookhaven National Lab. (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012704

OSTI ID:: 1475147

Report Number(s):: BNL-209110-2018-JAAM

Journal Information:: Journal of the Electrochemical Society, Vol. 165, Issue 11; ISSN 0013-4651

Publisher:: The Electrochemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 8 works

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Title: Capacity Retention for (De)lithiation of Silver Containing α-MnO2 : Impact of Structural Distortion and Transition Metal Dissolution

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Title: Capacity Retention for (De)lithiation of Silver Containing α-MnO₂ : Impact of Structural Distortion and Transition Metal Dissolution