Nanometer-scale mapping of irreversible electrochemical nucleation processes on solid Li-ion electrolytes

Amit Kumar; Thomas M. Arruda; Alexander Tselev; Ilia N. Ivanov; Jamie S. Lawton; Thomas A. Zawodzinski; Oleg Butyaev; Sergey Zayats; Stephen Jesse; Sergei V. Kalinin

doi:10.1038/srep01621

Nanometer-scale mapping of irreversible electrochemical nucleation processes on solid Li-ion electrolytes

Amit Kumar, Thomas M. Arruda, Alexander Tselev, Ilia N. Ivanov, Jamie S. Lawton, Thomas A. Zawodzinski, Oleg Butyaev, Sergey Zayats, Stephen Jesse, Sergei V. Kalinin

Center for Nanophase Matls Sciences

Research output: Contribution to journal › Article › peer-review

31 Scopus citations

Abstract

Electrochemical processes associated with changes in structure, connectivity or composition typically proceed via new phase nucleation with subsequent growth of nuclei. Understanding and controlling reactions requires the elucidation and control of nucleation mechanisms. However, factors controlling nucleation kinetics, including the interplay between local mechanical conditions, microstructure and local ionic profile remain inaccessible. Furthermore, the tendency of current probing techniques to interfere with the original microstructure prevents a systematic evaluation of the correlation between the microstructure and local electrochemical reactivity. In this work, the spatial variability of irreversible nucleation processes of Li on a Li-ion conductive glass-ceramics surface is studied with ∼30 nm resolution. An increased nucleation rate at the boundaries between the crystalline AlPO₄ phase and amorphous matrix is observed and attributed to Li segregation. This study opens a pathway for probing mechanisms at the level of single structural defects and elucidation of electrochemical activities in nanoscale volumes.

Original language	English
Article number	1621
Journal	Scientific Reports
Volume	3
DOIs	https://doi.org/10.1038/srep01621
State	Published - Apr 8 2013

Funding

Financial support for this project was provided by a Laboratory Directed Research and Development Program (LDRD). This research was conducted at the Center for Nanophase Materials Sciences, which is sponsored at Oak Ridge National Laboratory by the Scientific User Facilities Division, Office of Basic Energy Sciences, U.S. Department of Energy. JSL and TAZ acknowledge financial support from the NSF-funded TN-SCORE program, NSF EPS-1004083, under Thrust 2.

Funders	Funder number
NSF-funded
Scientific User Facilities Division
National Science Foundation	EPS-1004083
U.S. Department of Energy
Office of the Director	1004083
Basic Energy Sciences
Oak Ridge National Laboratory
Laboratory Directed Research and Development

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abstract = "Electrochemical processes associated with changes in structure, connectivity or composition typically proceed via new phase nucleation with subsequent growth of nuclei. Understanding and controlling reactions requires the elucidation and control of nucleation mechanisms. However, factors controlling nucleation kinetics, including the interplay between local mechanical conditions, microstructure and local ionic profile remain inaccessible. Furthermore, the tendency of current probing techniques to interfere with the original microstructure prevents a systematic evaluation of the correlation between the microstructure and local electrochemical reactivity. In this work, the spatial variability of irreversible nucleation processes of Li on a Li-ion conductive glass-ceramics surface is studied with ∼30 nm resolution. An increased nucleation rate at the boundaries between the crystalline AlPO4 phase and amorphous matrix is observed and attributed to Li segregation. This study opens a pathway for probing mechanisms at the level of single structural defects and elucidation of electrochemical activities in nanoscale volumes.",

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AU - Kumar, Amit

AU - Arruda, Thomas M.

AU - Tselev, Alexander

AU - Ivanov, Ilia N.

AU - Lawton, Jamie S.

AU - Zawodzinski, Thomas A.

AU - Butyaev, Oleg

AU - Zayats, Sergey

AU - Jesse, Stephen

AU - Kalinin, Sergei V.

PY - 2013/4/8

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N2 - Electrochemical processes associated with changes in structure, connectivity or composition typically proceed via new phase nucleation with subsequent growth of nuclei. Understanding and controlling reactions requires the elucidation and control of nucleation mechanisms. However, factors controlling nucleation kinetics, including the interplay between local mechanical conditions, microstructure and local ionic profile remain inaccessible. Furthermore, the tendency of current probing techniques to interfere with the original microstructure prevents a systematic evaluation of the correlation between the microstructure and local electrochemical reactivity. In this work, the spatial variability of irreversible nucleation processes of Li on a Li-ion conductive glass-ceramics surface is studied with ∼30 nm resolution. An increased nucleation rate at the boundaries between the crystalline AlPO4 phase and amorphous matrix is observed and attributed to Li segregation. This study opens a pathway for probing mechanisms at the level of single structural defects and elucidation of electrochemical activities in nanoscale volumes.

AB - Electrochemical processes associated with changes in structure, connectivity or composition typically proceed via new phase nucleation with subsequent growth of nuclei. Understanding and controlling reactions requires the elucidation and control of nucleation mechanisms. However, factors controlling nucleation kinetics, including the interplay between local mechanical conditions, microstructure and local ionic profile remain inaccessible. Furthermore, the tendency of current probing techniques to interfere with the original microstructure prevents a systematic evaluation of the correlation between the microstructure and local electrochemical reactivity. In this work, the spatial variability of irreversible nucleation processes of Li on a Li-ion conductive glass-ceramics surface is studied with ∼30 nm resolution. An increased nucleation rate at the boundaries between the crystalline AlPO4 phase and amorphous matrix is observed and attributed to Li segregation. This study opens a pathway for probing mechanisms at the level of single structural defects and elucidation of electrochemical activities in nanoscale volumes.

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Nanometer-scale mapping of irreversible electrochemical nucleation processes on solid Li-ion electrolytes

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