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Title: Revealing Anisotropic Spinel Formation on Pristine Li- and Mn-Rich Layered Oxide Surface and Its Impact on Cathode Performance

Abstract

Surface properties of cathode particles play important roles in the transport of ions and electrons and they may ultimately dominate cathode's performance and stability in lithium-ion batteries. Through the use of carefully prepared Li1.2Ni0.13Mn0.54Co0.13O2crystal samples with six distinct morphologies, surface transition-metal redox activities and crystal structural transformation are investigated as a function of surface area and surface crystalline orientation. Complementary depth-profiled core-level spectroscopy, namely, X-ray absorption spectroscopy, electron energy loss spectroscopy, and atomic-resolution scanning transmission electron microscopy, are applied in the study, presenting a fine example of combining advanced diagnostic techniques with a well-defined model system of battery materials. The present study reports the following findings: (1) a thin layer of defective spinel with reduced transition metals, similar to what is reported on cycled conventional secondary particles in the literature, is found on pristine oxide surface even before cycling, and (2) surface crystal structure and chemical composition of both pristine and cycled particles are facet dependent. Oxide structural and cycling stabilities improve with maximum expression of surface facets stable against transition-metal reduction. The intricate relationships among morphology, surface reactivity and structural transformation, electrochemical performance, and stability of the cathode materials are revealed.

Authors:
 [1];  [1];  [1];  [2];  [1]
+ Show Author Affiliations
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Energy Storage and Distributed Resources Division
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE); USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1369400
Alternate Identifier(s):
OSTI ID: 1400810; OSTI ID: 1458496
Grant/Contract Number:  
AC02-76SF00515; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Energy Materials
Additional Journal Information:
Journal Volume: 7; Journal Issue: 11; Journal ID: ISSN 1614-6832
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Kuppan, Saravanan, Shukla, Alpesh Khushalchand, Membreno, Daniel, Nordlund, Dennis, and Chen, Guoying. Revealing Anisotropic Spinel Formation on Pristine Li- and Mn-Rich Layered Oxide Surface and Its Impact on Cathode Performance. United States: N. p., 2017. Web. doi:10.1002/aenm.201602010.
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Kuppan, Saravanan, Shukla, Alpesh Khushalchand, Membreno, Daniel, Nordlund, Dennis, & Chen, Guoying. Revealing Anisotropic Spinel Formation on Pristine Li- and Mn-Rich Layered Oxide Surface and Its Impact on Cathode Performance. United States. https://doi.org/10.1002/aenm.201602010
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Kuppan, Saravanan, Shukla, Alpesh Khushalchand, Membreno, Daniel, Nordlund, Dennis, and Chen, Guoying. Fri . "Revealing Anisotropic Spinel Formation on Pristine Li- and Mn-Rich Layered Oxide Surface and Its Impact on Cathode Performance". United States. https://doi.org/10.1002/aenm.201602010. https://www.osti.gov/servlets/purl/1369400.
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@article{osti_1369400,
title = {Revealing Anisotropic Spinel Formation on Pristine Li- and Mn-Rich Layered Oxide Surface and Its Impact on Cathode Performance},
author = {Kuppan, Saravanan and Shukla, Alpesh Khushalchand and Membreno, Daniel and Nordlund, Dennis and Chen, Guoying},
abstractNote = {Surface properties of cathode particles play important roles in the transport of ions and electrons and they may ultimately dominate cathode's performance and stability in lithium-ion batteries. Through the use of carefully prepared Li1.2Ni0.13Mn0.54Co0.13O2crystal samples with six distinct morphologies, surface transition-metal redox activities and crystal structural transformation are investigated as a function of surface area and surface crystalline orientation. Complementary depth-profiled core-level spectroscopy, namely, X-ray absorption spectroscopy, electron energy loss spectroscopy, and atomic-resolution scanning transmission electron microscopy, are applied in the study, presenting a fine example of combining advanced diagnostic techniques with a well-defined model system of battery materials. The present study reports the following findings: (1) a thin layer of defective spinel with reduced transition metals, similar to what is reported on cycled conventional secondary particles in the literature, is found on pristine oxide surface even before cycling, and (2) surface crystal structure and chemical composition of both pristine and cycled particles are facet dependent. Oxide structural and cycling stabilities improve with maximum expression of surface facets stable against transition-metal reduction. The intricate relationships among morphology, surface reactivity and structural transformation, electrochemical performance, and stability of the cathode materials are revealed.},
doi = {10.1002/aenm.201602010},
journal = {Advanced Energy Materials},
number = 11,
volume = 7,
place = {United States},
year = {Fri Jan 06 00:00:00 EST 2017},
month = {Fri Jan 06 00:00:00 EST 2017}
}
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https://doi.org/10.1002/aenm.201602010
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    journal, January 2019

    • Pelegov, Dmitry V.; Nasara, Ralph Nicolai; Tu, Chia-hao
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    • DOI: 10.1039/c9cp04629a

    Spinel/Lithium‐Rich Manganese Oxide Hybrid Nanofibers as Cathode Materials for Rechargeable Lithium‐Ion Batteries
    journal, August 2019

    Injection of oxygen vacancies in the bulk lattice of layered cathodes
    journal, April 2019

    Effect of composition on the structure of lithium- and manganese-rich transition metal oxides
    journal, January 2018

    • Shukla, Alpesh Khushalchand; Ramasse, Quentin M.; Ophus, Colin
    • Energy & Environmental Science, Vol. 11, Issue 4
    • DOI: 10.1039/c7ee02443f

    High-discharge-voltage lithium-rich layered-oxide cathode materials based on low oxygen vacancy
    journal, January 2019

    • Zhang, Bin; Wang, Lve; Bai, Fan
    • Dalton Transactions, Vol. 48, Issue 10
    • DOI: 10.1039/c9dt00193j
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