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

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 Li 1.2Ni 0.13Mn 0.54Co 0.13O 2 crystal 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. Here, we report 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. Finally, 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]
  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:
Grant/Contract Number:
AC02-76SF00515; AC02-05CH11231
Type:
Accepted Manuscript
Journal Name:
Advanced Energy Materials
Additional Journal Information:
Journal Volume: 7; Journal Issue: 11; Journal ID: ISSN 1614-6832
Publisher:
Wiley
Research Org:
SLAC National Accelerator Lab., Menlo Park, CA (United States); Lawrence Berkeley National Lab. (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) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE
OSTI Identifier:
1369400
Alternate Identifier(s):
OSTI ID: 1400810; OSTI ID: 1458496

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., Web. doi:10.1002/aenm.201602010.
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. doi:10.1002/aenm.201602010.
Kuppan, Saravanan, Shukla, Alpesh Khushalchand, Membreno, Daniel, Nordlund, Dennis, and Chen, Guoying. 2017. "Revealing Anisotropic Spinel Formation on Pristine Li- and Mn-Rich Layered Oxide Surface and Its Impact on Cathode Performance". United States. doi:10.1002/aenm.201602010. https://www.osti.gov/servlets/purl/1369400.
@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 Li1.2Ni0.13Mn0.54Co0.13O2 crystal 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. Here, we report 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. Finally, 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 = {2017},
month = {1}
}

Works referenced in this record:

The significance of the Li2MnO3 component in ‘composite’ xLi2MnO3·(1−x)LiMn0.5Ni0.5O2 electrodes
journal, October 2004

Enhancing the rate capability of high capacity xLi2MnO3 · (1−x)LiMO2 (M=Mn, Ni, Co) electrodes by Li–Ni–PO4 treatment
journal, April 2009

Electrochemical and Structural Properties of xLi2M‘O3 ·(1− x )LiMn0.5Ni0.5O2 Electrodes for Lithium Batteries (M‘ = Ti, Mn, Zr; 0 ≤ x ⩽ 0.3)
journal, May 2004
  • Kim, Jeom-Soo; Johnson, Christopher S.; Vaughey, John T.
  • Chemistry of Materials, Vol. 16, Issue 10, p. 1996-2006
  • DOI: 10.1021/cm0306461