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Title: Revisiting Primary Particles in Layered Lithium Transition‐Metal Oxides and Their Impact on Structural Degradation

Abstract

Layered lithium transition-metal oxide materials, e.g., Li(Ni1-x-yCoxMny)O2 (NCM) and Li(Ni1-x-yCoxAly)O2, are the most promising candidates for lithium-ion battery cathodes. They generally consist of ≈10 µm spherical particles densely packed with smaller particles (0.1–1 µm), called secondary and primary particles, respectively. The micrometer- to nanometer-sized particles are critical to the battery performance because they affect the reaction capability of the cathode. Herein, the crystal structure of the primary particles of NCM materials is revisited. Elaborate transmission electron microscopy investigations reveal that the so-called primary particles, often considered as single crystals, are in fact polycrystalline secondary particles. They contain low-angle and exceptionally stable special grain boundaries (GBs) presumably created during aggregation via an oriented attachment mechanism. Thus, this so-called primary particle is renamed as primary-like particle. More importantly, the low-angle GBs between the smaller true primary particles cause the development of nanocracks within the primary-like particles of Ni-rich NCM cathodes after repetitive electrochemical cycles. Moreover, in rectifying a prevalent misconception about primary particles, this study provides a previously unknown but important origin of structural degradation in Ni-rich layered cathodes.

Authors:
 [1];  [2];  [3];  [3];  [3];  [3];  [2];  [4];  [2]
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  1. Department of Materials Science and Engineering and Research Institute of Advanced Materials Seoul National University Seoul 08826 Republic of Korea, Condensed Matter Physics and Materials Science Department Brookhaven National Laboratory Upton NY 11973 USA
  2. Department of Materials Science and Engineering and Research Institute of Advanced Materials Seoul National University Seoul 08826 Republic of Korea
  3. AE Group Platform Technology Lab Samsung Advanced Institute of Technology Suwon‐si Gyeonggi‐do 443‐803 Republic of Korea
  4. Condensed Matter Physics and Materials Science Department Brookhaven National Laboratory Upton NY 11973 USA
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1492094
Alternate Identifier(s):
OSTI ID: 1492095; OSTI ID: 1526690
Report Number(s):
BNL-211779-2019-JAAM
Journal ID: ISSN 2198-3844; 1800843
Grant/Contract Number:  
DESC0012704; SC0012704
Resource Type:
Published Article
Journal Name:
Advanced Science
Additional Journal Information:
Journal Name: Advanced Science Journal Volume: 6 Journal Issue: 6; Journal ID: ISSN 2198-3844
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; ithium-ion battery; layered lithium transition-metal oxide; primary particle; transmission electron microscopy; mechanical crack

Citation Formats

Lee, Seung‐Yong, Park, Gyeong‐Su, Jung, Changhoon, Ko, Dong‐Su, Park, Seong‐Yong, Kim, Hee Goo, Hong, Seong‐Hyeon, Zhu, Yimei, and Kim, Miyoung. Revisiting Primary Particles in Layered Lithium Transition‐Metal Oxides and Their Impact on Structural Degradation. Germany: N. p., 2019. Web. doi:10.1002/advs.201800843.
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Lee, Seung‐Yong, Park, Gyeong‐Su, Jung, Changhoon, Ko, Dong‐Su, Park, Seong‐Yong, Kim, Hee Goo, Hong, Seong‐Hyeon, Zhu, Yimei, & Kim, Miyoung. Revisiting Primary Particles in Layered Lithium Transition‐Metal Oxides and Their Impact on Structural Degradation. Germany. https://doi.org/10.1002/advs.201800843
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Lee, Seung‐Yong, Park, Gyeong‐Su, Jung, Changhoon, Ko, Dong‐Su, Park, Seong‐Yong, Kim, Hee Goo, Hong, Seong‐Hyeon, Zhu, Yimei, and Kim, Miyoung. Fri . "Revisiting Primary Particles in Layered Lithium Transition‐Metal Oxides and Their Impact on Structural Degradation". Germany. https://doi.org/10.1002/advs.201800843.
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@article{osti_1492094,
title = {Revisiting Primary Particles in Layered Lithium Transition‐Metal Oxides and Their Impact on Structural Degradation},
author = {Lee, Seung‐Yong and Park, Gyeong‐Su and Jung, Changhoon and Ko, Dong‐Su and Park, Seong‐Yong and Kim, Hee Goo and Hong, Seong‐Hyeon and Zhu, Yimei and Kim, Miyoung},
abstractNote = {Layered lithium transition-metal oxide materials, e.g., Li(Ni1-x-yCoxMny)O2 (NCM) and Li(Ni1-x-yCoxAly)O2, are the most promising candidates for lithium-ion battery cathodes. They generally consist of ≈10 µm spherical particles densely packed with smaller particles (0.1–1 µm), called secondary and primary particles, respectively. The micrometer- to nanometer-sized particles are critical to the battery performance because they affect the reaction capability of the cathode. Herein, the crystal structure of the primary particles of NCM materials is revisited. Elaborate transmission electron microscopy investigations reveal that the so-called primary particles, often considered as single crystals, are in fact polycrystalline secondary particles. They contain low-angle and exceptionally stable special grain boundaries (GBs) presumably created during aggregation via an oriented attachment mechanism. Thus, this so-called primary particle is renamed as primary-like particle. More importantly, the low-angle GBs between the smaller true primary particles cause the development of nanocracks within the primary-like particles of Ni-rich NCM cathodes after repetitive electrochemical cycles. Moreover, in rectifying a prevalent misconception about primary particles, this study provides a previously unknown but important origin of structural degradation in Ni-rich layered cathodes.},
doi = {10.1002/advs.201800843},
journal = {Advanced Science},
number = 6,
volume = 6,
place = {Germany},
year = {Fri Jan 25 00:00:00 EST 2019},
month = {Fri Jan 25 00:00:00 EST 2019}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1002/advs.201800843
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Cited by: 53 works
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Figures / Tables:

Figure 1 Figure 1: (a) Description of the structural terms of layered lithium transition-metal oxide cathode materials. (b–e) Scanning electron microscopy (SEM) images of pristine (b, c) Li(Ni0.33Co0.33Mn0.33)O2 (NCM 111) and (d, e) Li(Ni0.8Co0.1Mn0.1)O2 (NCM 811) cathode materials. (f) Atomic-resolution high-angle annular dark-field (HAADF) (left) and annular bright-field scanning transmission electron microscopymore » (ABF-STEM) (right) images of pristine NCM materials aligned along the [100] direction. An atomic model structure is superimposed on the image. (g) Enlarged atomic model structure of the NCM material viewed along the [100] direction based on ICDD No.00-056-0147.« less
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Works referenced in this record:

Nickel-Rich Layered Lithium Transition-Metal Oxide for High-Energy Lithium-Ion Batteries
journal, March 2015

  • Liu, Wen; Oh, Pilgun; Liu, Xien
  • Angewandte Chemie International Edition, Vol. 54, Issue 15
  • DOI: 10.1002/anie.201409262

Observation of Microstructural Evolution in Li Battery Cathode Oxide Particles by In Situ Electron Microscopy
journal, May 2013

  • Miller, Dean J.; Proff, Christian; Wen, J. G.
  • Advanced Energy Materials, Vol. 3, Issue 8
  • DOI: 10.1002/aenm.201300015

Direction-Specific Interactions Control Crystal Growth by Oriented Attachment
journal, May 2012

Mechanism of Formation of Monodispersed Colloids by Aggregation of Nanosize Precursors
journal, May 1999

  • Privman, Vladimir; Goia, Dan V.; Park, Jongsoon
  • Journal of Colloid and Interface Science, Vol. 213, Issue 1
  • DOI: 10.1006/jcis.1999.6106

Higher-Order Organization by Mesoscale Self-Assembly and Transformation of Hybrid Nanostructures
journal, May 2003

  • Cölfen, Helmut; Mann, Stephen
  • Angewandte Chemie International Edition, Vol. 42, Issue 21
  • DOI: 10.1002/anie.200200562

Electrochemical performance studies of Li-rich cathode materials with different primary particle sizes
journal, April 2014

Imperfect Oriented Attachment: Dislocation Generation in Defect-Free Nanocrystals
journal, August 1998

Review—High-Capacity Li[Ni 1- x Co x /2 Mn x /2 ]O 2 ( x = 0.1, 0.05, 0) Cathodes for Next-Generation Li-Ion Battery
journal, January 2015

  • Yoon, Chong S.; Choi, Moon Ho; Lim, Byung-Beom
  • Journal of The Electrochemical Society, Vol. 162, Issue 14
  • DOI: 10.1149/2.0101514jes

Electrochemical properties of LiNi1/3Co1/3Mn1/3O2 cathode material modified by coating with Al2O3 nanoparticles
journal, December 2014

Surface reconstruction and chemical evolution of stoichiometric layered cathode materials for lithium-ion batteries
journal, March 2014

  • Lin, Feng; Markus, Isaac M.; Nordlund, Dennis
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms4529

Metal segregation in hierarchically structured cathode materials for high-energy lithium batteries
journal, January 2016

Unraveling the Origin of Instability in Ni-Rich LiNi 1–2 x Co x Mn x O 2 (NCM) Cathode Materials
journal, March 2016

  • Liang, Chaoping; Kong, Fantai; Longo, Roberto C.
  • The Journal of Physical Chemistry C, Vol. 120, Issue 12
  • DOI: 10.1021/acs.jpcc.6b00369

High-energy-density lithium-ion battery using a carbon-nanotube–Si composite anode and a compositionally graded Li[Ni 0.85 Co 0.05 Mn 0.10 ]O 2 cathode
journal, January 2016

  • Lee, Joo Hyeong; Yoon, Chong S.; Hwang, Jang-Yeon
  • Energy & Environmental Science, Vol. 9, Issue 6
  • DOI: 10.1039/C6EE01134A

Theoretical Interpretation of Moiré Patterns
journal, January 1964

  • Oster, Gerald; Wasserman, Mark; Zwerling, Craig
  • Journal of the Optical Society of America, Vol. 54, Issue 2
  • DOI: 10.1364/JOSA.54.000169

Layered lithium transition metal oxide cathodes towards high energy lithium-ion batteries
journal, January 2012

  • He, Ping; Yu, Haijun; Li, De
  • Journal of Materials Chemistry, Vol. 22, Issue 9
  • DOI: 10.1039/c2jm14305d

Crystal Habit-Tuned Nanoplate Material of Li[Li1/3-2x/3NixMn2/3-x/3]O2 for High-Rate Performance Lithium-Ion Batteries
journal, August 2010

Structural and Chemical Evolution of Li- and Mn-Rich Layered Cathode Material
journal, February 2015

  • Zheng, Jianming; Xu, Pinghong; Gu, Meng
  • Chemistry of Materials, Vol. 27, Issue 4
  • DOI: 10.1021/cm5045978

Understanding the Degradation Mechanisms of LiNi 0.5 Co 0.2 Mn 0.3 O 2 Cathode Material in Lithium Ion Batteries
journal, August 2013

  • Jung, Sung-Kyun; Gwon, Hyeokjo; Hong, Jihyun
  • Advanced Energy Materials, Vol. 4, Issue 1
  • DOI: 10.1002/aenm.201300787

Intragranular cracking as a critical barrier for high-voltage usage of layer-structured cathode for lithium-ion batteries
journal, January 2017

  • Yan, Pengfei; Zheng, Jianming; Gu, Meng
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms14101

Li-ion battery materials: present and future
journal, June 2015

Coupled microstructural observations and local texture measurements with an automated crystallographic orientation mapping tool attached to a tem
journal, October 2005

  • Rauch, E. F.; Veron, M.
  • Materialwissenschaft und Werkstofftechnik, Vol. 36, Issue 10, p. 552-556
  • DOI: 10.1002/mawe.200500923

Deformation and stress in electrode materials for Li-ion batteries
journal, June 2014

Improving the Cycling Performance of the Layered Ni-Rich Oxide Cathode by Introducing Low-Content Li 2 MnO 3
journal, January 2016

Nickel-Rich Layered Cathode Materials for Automotive Lithium-Ion Batteries: Achievements and Perspectives
journal, December 2016

Intrinsic Origins of Crack Generation in Ni-rich LiNi0.8Co0.1Mn0.1O2 Layered Oxide Cathode Material
journal, January 2017

  • Lim, Jin-Myoung; Hwang, Taesoon; Kim, Duho
  • Scientific Reports, Vol. 7, Issue 1
  • DOI: 10.1038/srep39669

Nonclassical nucleation and growth of inorganic nanoparticles
journal, June 2016

Microscopically porous, interconnected single crystal LiNi1/3Co1/3Mn1/3O2 cathode material for Lithium ion batteries
journal, January 2011

  • Huang, Zhen-Dong; Liu, Xian-Ming; Oh, Sei-Woon
  • Journal of Materials Chemistry, Vol. 21, Issue 29
  • DOI: 10.1039/c1jm00059d

A review of Ni-based layered oxides for rechargeable Li-ion batteries
journal, January 2017

  • Xu, Jing; Lin, Feng; Doeff, Marca M.
  • Journal of Materials Chemistry A, Vol. 5, Issue 3
  • DOI: 10.1039/C6TA07991A

Oriented attachment and mesocrystals: Non-classical crystallization mechanisms based on nanoparticle assembly
journal, January 2006

  • Niederberger, Markus; Cölfen, Helmut
  • Phys. Chem. Chem. Phys., Vol. 8, Issue 28
  • DOI: 10.1039/B604589H

Structural Changes and Microstrain Generated on LiNi 0.80 Co 0.15 Al 0.05 O 2 during Cycling: Effects on the Electrochemical Performance
journal, January 2015

  • Robert, Rosa; Novák, Petr
  • Journal of The Electrochemical Society, Vol. 162, Issue 9
  • DOI: 10.1149/2.0721509jes

Enhancing Interfacial Bonding between Anisotropically Oriented Grains Using a Glue-Nanofiller for Advanced Li-Ion Battery Cathode
journal, April 2016

A perspective on nickel-rich layered oxide cathodes for lithium-ion batteries
journal, January 2017

Hydrogen peroxide assisted synthesis of LiNi1/3Co1/3Mn1/3O2 as high-performance cathode for lithium-ion batteries
journal, April 2015

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