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Title: Direct observation of defect-aided structural evolution in Ni-rich layered cathode

Abstract

Ni-rich LiNi1-x-yMnxCoyO2 (NMC) layered compounds have become the dominated cathode for lithium ion batteries. The role of crystallographic defects on their structure evolution and consequent performance degradation during electrochemical cycling is not yet fully understood. In this work, we investigated the structural evolution of Ni-rich NMC cathode in a solid-state cell via in-situ transmission electron microscopy. We identified antiphase boundary (APB) and twin boundary (TB) separating layered phases played an important role on phase change. Upon the lithium depletion, the APB extends across the layered structure, while Li/transition metal (TM) ion mixing in the layered phases is detected to induce the rock-salt phase formation along the coherent TB. According to DFT calculations, Li/TM mixing and phase transition are aided by the low diffusion barriers of TM ions at planar defects. Finally, this work reveals the dynamical scenario of secondary phase evolution, which helps to unveil the origin of performance fading in Ni-rich NMC.

Authors:
 [1];  [2];  [3];  [4];  [5]; ORCiD logo [6];  [7];  [5];  [8];  [7];  [9];  [10]
  1. Wenzhou Univ. (China); Univ. of Waterloo, ON (Canada); Brookhaven National Lab. (BNL), Upton, NY (United States)
  2. Harvard Univ., Cambridge, MA (United States); Univ. of Toronto, ON (Canada)
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Xiamen Univ., Fujian (China)
  4. Northwestern Polytechnical Univ., Xian (China)
  5. Stony Brook Univ., NY (United States)
  6. Brookhaven National Lab. (BNL), Upton, NY (United States)
  7. Wenzhou Univ. (China)
  8. Chinese Academy of Sciences (CAS), Beijing (China)
  9. Univ. of Waterloo, ON (Canada)
  10. Brookhaven National Lab. (BNL), Upton, NY (United States); Chinese Academy of Sciences (CAS), Beijing (China)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); University of Waterloo; Wenzhou University; National Natural Science Foundation of China (NSFC)
OSTI Identifier:
1647563
Alternate Identifier(s):
OSTI ID: 1786037
Report Number(s):
BNL-216254-2020-JAAM
Journal ID: ISSN 1433-7851
Grant/Contract Number:  
SC0012704; U1909213; 51772219; 51872209
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 59; Journal Issue: 49; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; in situ TEM; lithium ion batteries; cathode; defect; structural evolution

Citation Formats

Li, Shang, Yao, Zhenpeng, Zheng, Jianming, Fu, Maosen, Cen, Jiajie, Hwang, Sooyeon, Jin, Huile, Orlov, Alexander, Gu, Lin, Wang, Shun, Chen, Zhongwei, and Su, Dong. Direct observation of defect-aided structural evolution in Ni-rich layered cathode. United States: N. p., 2020. Web. https://doi.org/10.1002/anie.202008144.
Li, Shang, Yao, Zhenpeng, Zheng, Jianming, Fu, Maosen, Cen, Jiajie, Hwang, Sooyeon, Jin, Huile, Orlov, Alexander, Gu, Lin, Wang, Shun, Chen, Zhongwei, & Su, Dong. Direct observation of defect-aided structural evolution in Ni-rich layered cathode. United States. https://doi.org/10.1002/anie.202008144
Li, Shang, Yao, Zhenpeng, Zheng, Jianming, Fu, Maosen, Cen, Jiajie, Hwang, Sooyeon, Jin, Huile, Orlov, Alexander, Gu, Lin, Wang, Shun, Chen, Zhongwei, and Su, Dong. Sun . "Direct observation of defect-aided structural evolution in Ni-rich layered cathode". United States. https://doi.org/10.1002/anie.202008144. https://www.osti.gov/servlets/purl/1647563.
@article{osti_1647563,
title = {Direct observation of defect-aided structural evolution in Ni-rich layered cathode},
author = {Li, Shang and Yao, Zhenpeng and Zheng, Jianming and Fu, Maosen and Cen, Jiajie and Hwang, Sooyeon and Jin, Huile and Orlov, Alexander and Gu, Lin and Wang, Shun and Chen, Zhongwei and Su, Dong},
abstractNote = {Ni-rich LiNi1-x-yMnxCoyO2 (NMC) layered compounds have become the dominated cathode for lithium ion batteries. The role of crystallographic defects on their structure evolution and consequent performance degradation during electrochemical cycling is not yet fully understood. In this work, we investigated the structural evolution of Ni-rich NMC cathode in a solid-state cell via in-situ transmission electron microscopy. We identified antiphase boundary (APB) and twin boundary (TB) separating layered phases played an important role on phase change. Upon the lithium depletion, the APB extends across the layered structure, while Li/transition metal (TM) ion mixing in the layered phases is detected to induce the rock-salt phase formation along the coherent TB. According to DFT calculations, Li/TM mixing and phase transition are aided by the low diffusion barriers of TM ions at planar defects. Finally, this work reveals the dynamical scenario of secondary phase evolution, which helps to unveil the origin of performance fading in Ni-rich NMC.},
doi = {10.1002/anie.202008144},
journal = {Angewandte Chemie (International Edition)},
number = 49,
volume = 59,
place = {United States},
year = {2020},
month = {8}
}

Works referenced in this record:

Issues and challenges facing rechargeable lithium batteries
journal, November 2001

  • Tarascon, J.-M.; Armand, M.
  • Nature, Vol. 414, Issue 6861, p. 359-367
  • DOI: 10.1038/35104644

Challenges in the development of advanced Li-ion batteries: a review
journal, January 2011

  • Etacheri, Vinodkumar; Marom, Rotem; Elazari, Ran
  • Energy & Environmental Science, Vol. 4, Issue 9
  • DOI: 10.1039/c1ee01598b

Practical Evaluation of Li-Ion Batteries
journal, April 2019


Challenges for Rechargeable Li Batteries
journal, February 2010

  • Goodenough, John B.; Kim, Youngsik
  • Chemistry of Materials, Vol. 22, Issue 3, p. 587-603
  • DOI: 10.1021/cm901452z

Promise and reality of post-lithium-ion batteries with high energy densities
journal, March 2016


Electrodes with High Power and High Capacity for Rechargeable Lithium Batteries
journal, February 2006

  • Kang, Kisuk; Shirley Meng, Ying; Breger, Julien
  • Science, Vol. 311, Issue 5763, p. 977-980
  • DOI: 10.1126/science.1122152

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

The Impact of Electrolyte Additives and Upper Cut-off Voltage on the Formation of a Rocksalt Surface Layer in LiNi 0.8 Mn 0.1 Co 0.1 O 2 Electrodes
journal, January 2017

  • Li, Jing; Liu, Hanshuo; Xia, Jian
  • Journal of The Electrochemical Society, Vol. 164, Issue 4
  • DOI: 10.1149/2.0651704jes

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

Nickel-reiche Lithium-Übergangsmetall-Schichtverbindungen für Hochenergie-Lithiumionenakkumulatoren
journal, March 2015


Nickel-Rich and Lithium-Rich Layered Oxide Cathodes: Progress and Perspectives
journal, October 2015

  • Manthiram, Arumugam; Knight, James C.; Myung, Seung-Taek
  • Advanced Energy Materials, Vol. 6, Issue 1
  • DOI: 10.1002/aenm.201501010

Origin of Structural Evolution in Capacity Degradation for Overcharged NMC622 via Operando Coupled Investigation
journal, July 2017

  • Wang, Qi; Shen, Chong-Heng; Shen, Shou-Yu
  • ACS Applied Materials & Interfaces, Vol. 9, Issue 29
  • DOI: 10.1021/acsami.7b06326

Degradation Mechanisms and Mitigation Strategies of Nickel-Rich NMC-Based Lithium-Ion Batteries
journal, October 2019


Phosphorus Enrichment as a New Composition in the Solid Electrolyte Interphase of High-Voltage Cathodes and Its Effects on Battery Cycling
journal, October 2015


Electrolytes and Interphases in Li-Ion Batteries and Beyond
journal, October 2014


Degradation mechanisms of C6/LiNi0.5Mn0.3Co0.2O2 Li-ion batteries unraveled by non-destructive and post-mortem methods
journal, March 2019


High Voltage Operation of Ni-Rich NMC Cathodes Enabled by Stable Electrode/Electrolyte Interphases
journal, March 2018

  • Zhao, Wengao; Zheng, Jianming; Zou, Lianfeng
  • Advanced Energy Materials, Vol. 8, Issue 19
  • DOI: 10.1002/aenm.201800297

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

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

A New Type of Protective Surface Layer for High-Capacity Ni-Based Cathode Materials: Nanoscaled Surface Pillaring Layer
journal, February 2013

  • Cho, Yonghyun; Oh, Pilgun; Cho, Jaephil
  • Nano Letters, Vol. 13, Issue 3
  • DOI: 10.1021/nl304558t

Degradation effects on the surface of commercial LiNi 0.5 Co 0.2 Mn 0.3 O 2 electrodes
journal, December 2016


Ni/Li Disordering in Layered Transition Metal Oxide: Electrochemical Impact, Origin, and Control
journal, June 2019


Coupling of electrochemically triggered thermal and mechanical effects to aggravate failure in a layered cathode
journal, June 2018


Rock-Salt Growth-Induced (003) Cracking in a Layered Positive Electrode for Li-Ion Batteries
journal, October 2017


Factors that affect Li mobility in layered lithium transition metal oxides
journal, September 2006


Unlocking the Potential of Cation-Disordered Oxides for Rechargeable Lithium Batteries
journal, January 2014


Formation of the Spinel Phase in the Layered Composite Cathode Used in Li-Ion Batteries
journal, December 2012

  • Gu, Meng; Belharouak, Ilias; Zheng, Jianming
  • ACS Nano, Vol. 7, Issue 1
  • DOI: 10.1021/nn305065u

First-Principles Calculations of Lithium-Ion Migration at a Coherent Grain Boundary in a Cathode Material, LiCoO 2
journal, November 2012

  • Moriwake, Hiroki; Kuwabara, Akihide; Fisher, Craig A. J.
  • Advanced Materials, Vol. 25, Issue 4
  • DOI: 10.1002/adma.201202805

Formation, Structural Variety, and Impact of Antiphase Boundaries on Li Diffusion in LiCoO 2 Thin-Film Cathodes
journal, September 2018

  • Ong, Phuong-Vu; Yang, Zhenzhong; Sushko, Peter V.
  • The Journal of Physical Chemistry Letters, Vol. 9, Issue 18
  • DOI: 10.1021/acs.jpclett.8b02185

Dynamic imaging of crystalline defects in lithium-manganese oxide electrodes during electrochemical activation to high voltage
journal, April 2019


In Situ Atomic-Scale Observation of Electrochemical Delithiation Induced Structure Evolution of LiCoO 2 Cathode in a Working All-Solid-State Battery
journal, March 2017

  • Gong, Yue; Zhang, Jienan; Jiang, Liwei
  • Journal of the American Chemical Society, Vol. 139, Issue 12
  • DOI: 10.1021/jacs.6b13344

Three-dimensional atomic-scale observation of structural evolution of cathode material in a working all-solid-state battery
journal, August 2018


Structural Changes and Thermal Stability of Charged LiNi x Mn y Co z O 2 Cathode Materials Studied by Combined In Situ Time-Resolved XRD and Mass Spectroscopy
journal, December 2014

  • Bak, Seong-Min; Hu, Enyuan; Zhou, Yongning
  • ACS Applied Materials & Interfaces, Vol. 6, Issue 24
  • DOI: 10.1021/am506712c

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

Synthesis of Li-Rich NMC: A Comprehensive Study
journal, November 2017


Direct Visualization of Li Dendrite Effect on LiCoO 2 Cathode by In Situ TEM
journal, November 2018


Evolution of Structure and Lithium Dynamics in LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) Cathodes during Electrochemical Cycling
journal, March 2019


Study of the Failure Mechanisms of LiNi 0.8 Mn 0.1 Co 0.1 O 2 Cathode Material for Lithium Ion Batteries
journal, January 2015

  • Li, Jing; Downie, Laura E.; Ma, Lin
  • Journal of The Electrochemical Society, Vol. 162, Issue 7
  • DOI: 10.1149/2.1011507jes

First Evidence of Manganese–Nickel Segregation and Densification upon Cycling in Li-Rich Layered Oxides for Lithium Batteries
journal, July 2013

  • Boulineau, Adrien; Simonin, Loïc; Colin, Jean-François
  • Nano Letters, Vol. 13, Issue 8
  • DOI: 10.1021/nl4019275

Microstructural Observation of LiNi 0.8 Co 0.15 Al 0.05 O 2 after Charge and Discharge by Scanning Transmission Electron Microscopy
journal, January 2012

  • Makimura, Yoshinari; Zheng, Shijian; Ikuhara, Yuichi
  • Journal of The Electrochemical Society, Vol. 159, Issue 7
  • DOI: 10.1149/2.073207jes

Layered Mixed Transition Metal Oxide Cathodes with Reduced Cobalt Content for Lithium Ion Batteries
journal, December 2008

  • Xiao, Jie; Chernova, Natasha A.; Whittingham, M. Stanley
  • Chemistry of Materials, Vol. 20, Issue 24
  • DOI: 10.1021/cm802316d

Particle Size Dependence of the Ionic Diffusivity
journal, October 2010

  • Malik, Rahul; Burch, Damian; Bazant, Martin
  • Nano Letters, Vol. 10, Issue 10
  • DOI: 10.1021/nl1023595