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Title: Visualization of lithium-ion transport and phase evolution within and between manganese oxide nanorods

Abstract

Multiple lithium-ion transport pathways and local phase changes upon lithiation in silver hollandite are revealed via in situ microscopy including electron diffraction, imaging and spectroscopy, coupled with density functional theory and phase field calculations. Here, we report unexpected inter-nanorod lithium-ion transport, where the reaction fronts and kinetics are maintained within the neighbouring nanorod. Notably, this is the first time-resolved visualization of lithium-ion transport within and between individual nanorods, where the impact of oxygen deficiencies is delineated. Initially, fast lithium-ion transport is observed along the long axis with small net volume change, resulting in two lithiated silver hollandite phases distinguishable by orthorhombic distortion. As a result, a slower reaction front is observed, with formation of polyphase lithiated silver hollandite and face-centred-cubic silver metal with substantial volume expansion. Our results indicate lithium-ion transport is not confined within a single nanorod and may provide a paradigm shift for one-dimensional tunnelled materials, particularly towards achieving high-rate capability.

Authors:
 [1];  [2];  [2];  [3]; ORCiD logo [4];  [4];  [5]; ORCiD logo [6];  [7];  [8];  [7];  [9];  [2]
  1. Southeast Univ., Nanjing (China). SEU-FEI Nano-Pico Center; Brookhaven National Lab. (BNL), Upton, NY (United States). Condensed Matter Physics and Materials Science Dept.
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). Condensed Matter Physics and Materials Science Dept.
  3. Stony Brook Univ., NY (United States). Dept. of Physics and Astronomy
  4. Stony Brook Univ., NY (United States). Dept. of Chemistry
  5. Stony Brook Univ., NY (United States). Dept. of Physics and Astronomy and Inst. for Advanced Computational Science
  6. Southeast Univ., Nanjing (China). SEU-FEI Nano-Pico Center
  7. Stony Brook Univ., NY (United States). Dept. of Chemistry and Dept. of Materials Science and Engineering
  8. Stony Brook Univ., NY (United States). Dept. of Chemistry and Dept. of Materials Science and Engineering; Brookhaven National Lab. (BNL), Upton, NY (United States). Energy Sciences Directorate
  9. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1372453
Report Number(s):
BNL-114057-2017-JA
Journal ID: ISSN 2041-1723; R&D Project: MA015MACA; KC0201010
Grant/Contract Number:
SC00112704; SC0012673; SC0012704; AC02-05CH11231
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 8; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; 25 ENERGY STORAGE; batteries

Citation Formats

Xu, Feng, Wu, Lijun, Meng, Qingping, Kaltak, Merzuk, Huang, Jianping, Durham, Jessica L., Fernandez-Serra, Marivi, Sun, Litao, Marschilok, Amy C., Takeuchi, Esther S., Takeuchi, Kenneth J., Hybertsen, Mark S., and Zhu, Yimei. Visualization of lithium-ion transport and phase evolution within and between manganese oxide nanorods. United States: N. p., 2017. Web. doi:10.1038/ncomms15400.
Xu, Feng, Wu, Lijun, Meng, Qingping, Kaltak, Merzuk, Huang, Jianping, Durham, Jessica L., Fernandez-Serra, Marivi, Sun, Litao, Marschilok, Amy C., Takeuchi, Esther S., Takeuchi, Kenneth J., Hybertsen, Mark S., & Zhu, Yimei. Visualization of lithium-ion transport and phase evolution within and between manganese oxide nanorods. United States. doi:10.1038/ncomms15400.
Xu, Feng, Wu, Lijun, Meng, Qingping, Kaltak, Merzuk, Huang, Jianping, Durham, Jessica L., Fernandez-Serra, Marivi, Sun, Litao, Marschilok, Amy C., Takeuchi, Esther S., Takeuchi, Kenneth J., Hybertsen, Mark S., and Zhu, Yimei. Wed . "Visualization of lithium-ion transport and phase evolution within and between manganese oxide nanorods". United States. doi:10.1038/ncomms15400. https://www.osti.gov/servlets/purl/1372453.
@article{osti_1372453,
title = {Visualization of lithium-ion transport and phase evolution within and between manganese oxide nanorods},
author = {Xu, Feng and Wu, Lijun and Meng, Qingping and Kaltak, Merzuk and Huang, Jianping and Durham, Jessica L. and Fernandez-Serra, Marivi and Sun, Litao and Marschilok, Amy C. and Takeuchi, Esther S. and Takeuchi, Kenneth J. and Hybertsen, Mark S. and Zhu, Yimei},
abstractNote = {Multiple lithium-ion transport pathways and local phase changes upon lithiation in silver hollandite are revealed via in situ microscopy including electron diffraction, imaging and spectroscopy, coupled with density functional theory and phase field calculations. Here, we report unexpected inter-nanorod lithium-ion transport, where the reaction fronts and kinetics are maintained within the neighbouring nanorod. Notably, this is the first time-resolved visualization of lithium-ion transport within and between individual nanorods, where the impact of oxygen deficiencies is delineated. Initially, fast lithium-ion transport is observed along the long axis with small net volume change, resulting in two lithiated silver hollandite phases distinguishable by orthorhombic distortion. As a result, a slower reaction front is observed, with formation of polyphase lithiated silver hollandite and face-centred-cubic silver metal with substantial volume expansion. Our results indicate lithium-ion transport is not confined within a single nanorod and may provide a paradigm shift for one-dimensional tunnelled materials, particularly towards achieving high-rate capability.},
doi = {10.1038/ncomms15400},
journal = {Nature Communications},
number = ,
volume = 8,
place = {United States},
year = {Wed May 24 00:00:00 EDT 2017},
month = {Wed May 24 00:00:00 EDT 2017}
}

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