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Title: Revealing Grain-Boundary-Induced Degradation Mechanisms in Li-Rich Cathode Materials

Abstract

Despite their high energy densities, Li- and Mn-rich, layered-layered, xLi2MnO3center dot(1 - x)LiTMO2 (TM = Ni, Mn, Co) (LMR-NMC) cathodes require further development in order to overcome issues related to bulk and surface instabilities such as Mn dissolution, impedance rise, and voltage fade. One promising strategy to modify LMR-NMC properties has been the incorporation of spinel-type, local domains to create "layered- layered-spinel" cathodes. HoweVer, precise control of local structure and composition, as well as subsequent characterization of such materials, is challenging and elucidating structure-property relationships is not trivial. Therefore, detailed studies of atomic structures within these materials are still critical to their development. Herein, aberration corrected-scanning transmission electron microscopy (AC-STEM) is utilized to study atomic structures, prior to and subsequent to electrochemical cycling, of LMR-NMC materials having integrated spinel-type components. The results demonstrate that strained grain boundaries with various atomic configurations, including spinel-type structures, can exist. These high energy boundaries appear to induce cracking and promote dissolution of Mn by increasing the contact surface area to electrolyte as well as migration of Ni during cycling, thereby accelerating performance degradation. These results present insights into the important role that local structures can play in the macroscopic degradation of the cathode structuresmore » and reiterate the complexity of how synthesis and composition affect structure-electrochemical property relationships of advanced cathode designs.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2];  [1];  [2]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Univ. of Illinois, Chicago, IL (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1633305
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Nano Letters
Additional Journal Information:
Journal Volume: 20; Journal Issue: 2; Journal ID: ISSN 1530-6984
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Li-ion battery; Li-rich cathodes; STEM/EELS; grain boundary; layered oxide cathodes; structural degradation

Citation Formats

Sharifi-Asl, Soroosh, Yurkiv, Vitaliy, Gutierrez, Arturo, Cheng, Meng, Balasubramanian, Mahalingam, Mashayek, Farzad, Croy, Jason, and Shahbazian-Yassar, Reza. Revealing Grain-Boundary-Induced Degradation Mechanisms in Li-Rich Cathode Materials. United States: N. p., 2019. Web. https://doi.org/10.1021/acs.nanolett.9b04620.
Sharifi-Asl, Soroosh, Yurkiv, Vitaliy, Gutierrez, Arturo, Cheng, Meng, Balasubramanian, Mahalingam, Mashayek, Farzad, Croy, Jason, & Shahbazian-Yassar, Reza. Revealing Grain-Boundary-Induced Degradation Mechanisms in Li-Rich Cathode Materials. United States. https://doi.org/10.1021/acs.nanolett.9b04620
Sharifi-Asl, Soroosh, Yurkiv, Vitaliy, Gutierrez, Arturo, Cheng, Meng, Balasubramanian, Mahalingam, Mashayek, Farzad, Croy, Jason, and Shahbazian-Yassar, Reza. Mon . "Revealing Grain-Boundary-Induced Degradation Mechanisms in Li-Rich Cathode Materials". United States. https://doi.org/10.1021/acs.nanolett.9b04620. https://www.osti.gov/servlets/purl/1633305.
@article{osti_1633305,
title = {Revealing Grain-Boundary-Induced Degradation Mechanisms in Li-Rich Cathode Materials},
author = {Sharifi-Asl, Soroosh and Yurkiv, Vitaliy and Gutierrez, Arturo and Cheng, Meng and Balasubramanian, Mahalingam and Mashayek, Farzad and Croy, Jason and Shahbazian-Yassar, Reza},
abstractNote = {Despite their high energy densities, Li- and Mn-rich, layered-layered, xLi2MnO3center dot(1 - x)LiTMO2 (TM = Ni, Mn, Co) (LMR-NMC) cathodes require further development in order to overcome issues related to bulk and surface instabilities such as Mn dissolution, impedance rise, and voltage fade. One promising strategy to modify LMR-NMC properties has been the incorporation of spinel-type, local domains to create "layered- layered-spinel" cathodes. HoweVer, precise control of local structure and composition, as well as subsequent characterization of such materials, is challenging and elucidating structure-property relationships is not trivial. Therefore, detailed studies of atomic structures within these materials are still critical to their development. Herein, aberration corrected-scanning transmission electron microscopy (AC-STEM) is utilized to study atomic structures, prior to and subsequent to electrochemical cycling, of LMR-NMC materials having integrated spinel-type components. The results demonstrate that strained grain boundaries with various atomic configurations, including spinel-type structures, can exist. These high energy boundaries appear to induce cracking and promote dissolution of Mn by increasing the contact surface area to electrolyte as well as migration of Ni during cycling, thereby accelerating performance degradation. These results present insights into the important role that local structures can play in the macroscopic degradation of the cathode structures and reiterate the complexity of how synthesis and composition affect structure-electrochemical property relationships of advanced cathode designs.},
doi = {10.1021/acs.nanolett.9b04620},
journal = {Nano Letters},
number = 2,
volume = 20,
place = {United States},
year = {2019},
month = {12}
}

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