Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: In Situ Probing and Synthetic Control of Cationic Ordering in Ni-Rich Layered Oxide Cathodes

Abstract

Ni-rich layered oxides (LiNi1-xMxO2; M=Co, Mn, …) are appealing alternatives to conventional LiCoO2 as cathodes in Li-ion batteries for automobile and other large-scale applications due to their high theoretical capacity and low cost. However, preparing stoichiometric LiNi1-xMxO2 with ordered layer structure and high reversible capacity, has proven difficult due to Ni2+/Li+ cation mixing in octahedral sites. Herein, we report on in-situ studies of synthesis reactions and the associated structural ordering in preparing LiNiO2 and the Co-substituted variant, LiNi0.8Co0.2O2, thereby gaining insights into synthetic control of the structure and electrochemical properties of Ni-rich layered oxides. Results from this study indicate a direct transformation of the intermediate from the rock salt structure into hexagonal phase, and during the process, Co substitution facilities the nucleation of a Co-rich layered phase at low temperatures and subsequent growth and stabilization of solid solution Li(Ni, Co)O2 upon heat treatment in a highly oxidation environment. Optimal conditions were identified from the in-situ studies and utilized in obtaining stoichiometric LiNi0.8Co0.2O2 that exhibits high capacity of about 200 mAh/g with excellent retention. The findings shed light on designing Ni-rich layered oxide cathodes with enhanced electrochemical properties through synthetic control of the structural ordering in the materials.

Authors:
 [1];  [1];  [2];  [3];  [4];  [4];  [1];  [1];  [5];  [5];  [6];  [1];  [1]
+ Show Author Affiliations
  1. Brookhaven National Lab. (BNL), Upton, NY (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. Alfred Univ., NY (United States)
  4. Louisiana State Univ., Baton Rouge, LA (United States)
  5. Argonne National Lab. (ANL), Argonne, IL (United States)
  6. Peking Univ. Shenzhen Graduate School, Shenzhen (China)
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:
1768777
Alternate Identifier(s):
OSTI ID: 1389223; OSTI ID: 1401242
Report Number(s):
BNL-221104-2021-JAAM; BNL-114130-2017-JA
Journal ID: ISSN 1614-6832
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Energy Materials
Additional Journal Information:
Journal Volume: 7; Journal Issue: 3; Journal ID: ISSN 1614-6832
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 25 ENERGY STORAGE

Citation Formats

Zhao, Jianqing, Zhang, Wei, Huq, Ashfia, Misture, Scott T., Zhang, Boliang, Guo, Shengmin, Wu, Lijun, Zhu, Yimei, Chen, Zonghai, Amine, Khalil, Pan, Feng, Bai, Jianming, and Wang, Feng. In Situ Probing and Synthetic Control of Cationic Ordering in Ni-Rich Layered Oxide Cathodes. United States: N. p., 2016. Web. doi:10.1002/aenm.201601266.
Copy to clipboard
Zhao, Jianqing, Zhang, Wei, Huq, Ashfia, Misture, Scott T., Zhang, Boliang, Guo, Shengmin, Wu, Lijun, Zhu, Yimei, Chen, Zonghai, Amine, Khalil, Pan, Feng, Bai, Jianming, & Wang, Feng. In Situ Probing and Synthetic Control of Cationic Ordering in Ni-Rich Layered Oxide Cathodes. United States. https://doi.org/10.1002/aenm.201601266
Copy to clipboard
Zhao, Jianqing, Zhang, Wei, Huq, Ashfia, Misture, Scott T., Zhang, Boliang, Guo, Shengmin, Wu, Lijun, Zhu, Yimei, Chen, Zonghai, Amine, Khalil, Pan, Feng, Bai, Jianming, and Wang, Feng. Mon . "In Situ Probing and Synthetic Control of Cationic Ordering in Ni-Rich Layered Oxide Cathodes". United States. https://doi.org/10.1002/aenm.201601266. https://www.osti.gov/servlets/purl/1768777.
Copy to clipboard
@article{osti_1768777,
title = {In Situ Probing and Synthetic Control of Cationic Ordering in Ni-Rich Layered Oxide Cathodes},
author = {Zhao, Jianqing and Zhang, Wei and Huq, Ashfia and Misture, Scott T. and Zhang, Boliang and Guo, Shengmin and Wu, Lijun and Zhu, Yimei and Chen, Zonghai and Amine, Khalil and Pan, Feng and Bai, Jianming and Wang, Feng},
abstractNote = {Ni-rich layered oxides (LiNi1-xMxO2; M=Co, Mn, …) are appealing alternatives to conventional LiCoO2 as cathodes in Li-ion batteries for automobile and other large-scale applications due to their high theoretical capacity and low cost. However, preparing stoichiometric LiNi1-xMxO2 with ordered layer structure and high reversible capacity, has proven difficult due to Ni2+/Li+ cation mixing in octahedral sites. Herein, we report on in-situ studies of synthesis reactions and the associated structural ordering in preparing LiNiO2 and the Co-substituted variant, LiNi0.8Co0.2O2, thereby gaining insights into synthetic control of the structure and electrochemical properties of Ni-rich layered oxides. Results from this study indicate a direct transformation of the intermediate from the rock salt structure into hexagonal phase, and during the process, Co substitution facilities the nucleation of a Co-rich layered phase at low temperatures and subsequent growth and stabilization of solid solution Li(Ni, Co)O2 upon heat treatment in a highly oxidation environment. Optimal conditions were identified from the in-situ studies and utilized in obtaining stoichiometric LiNi0.8Co0.2O2 that exhibits high capacity of about 200 mAh/g with excellent retention. The findings shed light on designing Ni-rich layered oxide cathodes with enhanced electrochemical properties through synthetic control of the structural ordering in the materials.},
doi = {10.1002/aenm.201601266},
journal = {Advanced Energy Materials},
number = 3,
volume = 7,
place = {United States},
year = {Mon Oct 17 00:00:00 EDT 2016},
month = {Mon Oct 17 00:00:00 EDT 2016}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1002/aenm.201601266
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 188 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

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

Understanding local degradation of cycled Ni-rich cathode materials at high operating temperature for Li-ion batteries
journal, September 2014

  • Hwang, Sooyeon; Kim, Dong Hyun; Chung, Kyung Yoon
  • Applied Physics Letters, Vol. 105, Issue 10
  • DOI: 10.1063/1.4895336

Template-Synthesized LiCoO2, LiMn2O4, and LiNi0.8Co0.2O2 Nanotubes as the Cathode Materials of Lithium Ion Batteries.
journal, November 2005

On the LixNi0.8Co0.2O2System
journal, February 1998

Mechanism of carbothermal reduction of iron, cobalt, nickel and copper oxides
journal, September 2000

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

Effect of Ni 2+ Content on Lithium/Nickel Disorder for Ni-Rich Cathode Materials
journal, April 2015

  • Wu, Feng; Tian, Jun; Su, Yuefeng
  • ACS Applied Materials & Interfaces, Vol. 7, Issue 14
  • DOI: 10.1021/acsami.5b00645

An overview of the Li(Ni,M)O2 systems: syntheses, structures and properties
journal, September 1999

Structure Tracking Aided Design and Synthesis of Li 3 V 2 (PO 4 ) 3 Nanocrystals as High-Power Cathodes for Lithium Ion Batteries
journal, August 2015

Particle size effect of Ni-rich cathode materials on lithium ion battery performance
journal, January 2012

Kinetics Tuning of Li-Ion Diffusion in Layered Li(Ni x Mn y Co z )O 2
journal, June 2015

  • Wei, Yi; Zheng, Jiaxin; Cui, Suihan
  • Journal of the American Chemical Society, Vol. 137, Issue 26
  • DOI: 10.1021/jacs.5b04040

Synthesis and electrochemical properties of LiNi0.8Co0.2O2 nanopowders for lithium ion battery applications
journal, January 2011

A soft chemistry synthetic method for preparing LiNi0.8Co0.2O2 with enhanced electrochemical performances
journal, May 2010

  • Cao, Xiaoyu; Xie, Lingling; Wang, Ruijuan
  • Journal of Solid State Electrochemistry, Vol. 15, Issue 3
  • DOI: 10.1007/s10008-010-1107-8

Differentiating allotropic LiCoO2/Li2Co2O4: A structural and electrochemical study
journal, December 2014

Structural Origin of Overcharge-Induced Thermal Instability of Ni-Containing Layered-Cathodes for High-Energy-Density Lithium Batteries
journal, September 2011

  • Wu, Lijun; Nam, Kyung-Wan; Wang, Xiaojian
  • Chemistry of Materials, Vol. 23, Issue 17
  • DOI: 10.1021/cm201452q

Ultimate Limits to Intercalation Reactions for Lithium Batteries
journal, October 2014

  • Whittingham, M. Stanley
  • Chemical Reviews, Vol. 114, Issue 23
  • DOI: 10.1021/cr5003003

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

Effects of cationic substitution on structural defects in layered cathode materials LiNiO2
journal, January 2014

  • Chen, Hungru; Dawson, James A.; Harding, John H.
  • Journal of Materials Chemistry A, Vol. 2, Issue 21
  • DOI: 10.1039/c4ta00637b

Nanostructured high-energy cathode materials for advanced lithium batteries
journal, October 2012

  • Sun, Yang-Kook; Chen, Zonghai; Noh, Hyung-Joo
  • Nature Materials, Vol. 11, Issue 11
  • DOI: 10.1038/nmat3435

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

Conflicting Roles of Nickel in Controlling Cathode Performance in Lithium Ion Batteries
journal, September 2012

  • Gu, Meng; Belharouak, Ilias; Genc, Arda
  • Nano Letters, Vol. 12, Issue 10
  • DOI: 10.1021/nl302249v

Effects of Sintering Temperature on the Structure of the Layered Phase Li[sub x](Ni[sub 0.8]Co[sub 0.2])O2
journal, January 2000

  • Gover, Richard K. B.; Kanno, Ryoji; Mitchell, Brian J.
  • Journal of The Electrochemical Society, Vol. 147, Issue 11
  • DOI: 10.1149/1.1394016

Reaction Mechanism of LiNiO2 Synthesized in Oxygen Atmosphere by Pechini Method.
journal, January 2002

  • Lin, Shih-Pin; Fung, Kuan-Zong; Hon, Yi-Ming
  • Journal of the Ceramic Society of Japan, Vol. 110, Issue 1288
  • DOI: 10.2109/jcersj.110.1038

LiMO2 (M = Ni, Co) thin film cathode materials: a correlation between the valence state of transition metals and the electrochemical properties
journal, January 2014

  • Cherkashinin, G.; Ensling, D.; Jaegermann, W.
  • Journal of Materials Chemistry A, Vol. 2, Issue 10
  • DOI: 10.1039/c3ta14509c

Effect of Al Addition on Formation of Layer-Structured LiNiO2
journal, August 2002

  • Lin, Shih-Pin; Fung, Kuan-Zong; Hon, Yi-Ming
  • Journal of Solid State Chemistry, Vol. 167, Issue 1
  • DOI: 10.1006/jssc.2002.9624

Review—Li-Rich Layered Oxide Cathodes for Next-Generation Li-Ion Batteries: Chances and Challenges
journal, January 2015

  • Rozier, Patrick; Tarascon, Jean Marie
  • Journal of The Electrochemical Society, Vol. 162, Issue 14
  • DOI: 10.1149/2.0111514jes

Surface-modified concentration-gradient Ni-rich layered oxide cathodes for high-energy lithium-ion batteries
journal, May 2015

A New High Power LiNi 0.81 Co 0.1 Al 0.09 O 2 Cathode Material for Lithium-Ion Batteries
journal, April 2014

EXPGUI , a graphical user interface for GSAS
journal, April 2001

Various aspects of LiNiO 2 chemistry: A review
journal, January 2005

Nickel-Rich Layered Microspheres Cathodes: Lithium/Nickel Disordering and Electrochemical Performance
journal, September 2014

  • Fu, Chaochao; Li, Guangshe; Luo, Dong
  • ACS Applied Materials & Interfaces, Vol. 6, Issue 18
  • DOI: 10.1021/am5030726

Role of Mn Content on the Electrochemical Properties of Nickel-Rich Layered LiNi 0.8– x Co 0.1 Mn 0.1+ x O 2 (0.0 ≤ x ≤ 0.08) Cathodes for Lithium-Ion Batteries
journal, March 2015

  • Zheng, Jianming; Kan, Wang Hay; Manthiram, Arumugam
  • ACS Applied Materials & Interfaces, Vol. 7, Issue 12
  • DOI: 10.1021/acsami.5b00788

Electronic Structure of Lithium Nickel Oxides by Electron Energy Loss Spectroscopy
journal, June 2005

  • Koyama, Yukinori; Mizoguchi, Teruyasu; Ikeno, Hidekazu
  • The Journal of Physical Chemistry B, Vol. 109, Issue 21
  • DOI: 10.1021/jp050486b

Elucidation of the surface characteristics and electrochemistry of high-performance LiNiO 2
journal, January 2016

  • Xu, Jing; Lin, Feng; Nordlund, Dennis
  • Chemical Communications, Vol. 52, Issue 22
  • DOI: 10.1039/C5CC09434H

Electrochemical and in-situ XRD characterization of LiNiO2 and LiCo0.2Ni0.8O2 electrodes for rechargeable lithium cells
journal, November 1999

Changes in the Cation Ordering of Layered O3 LixNi0.5Mn0.5O2 during Electrochemical Cycling to High Voltages:  An Electron Diffraction Study
journal, April 2007

  • Li, Hayley H.; Yabuuchi, Naoaki; Meng, Ying S.
  • Chemistry of Materials, Vol. 19, Issue 10
  • DOI: 10.1021/cm070139+

Effect of cobalt substitution on cationic distribution in LiNi1 − y CoyO2 electrode materials
journal, September 1996

The Effect on Cathode Performance of Oxygen Non-Stoichiometry and Interlayer Mixing in Layered Rock Salt LiNi 0.8 Mn 0.1 Co 0.1 O 2-δ
journal, January 2012

  • Idris, M. Sobri; West, A. R.
  • Journal of The Electrochemical Society, Vol. 159, Issue 4
  • DOI: 10.1149/2.037204jes

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

Design of Nickel-rich Layered Oxides Using d Electronic Donor for Redox Reactions
journal, September 2015

Cobalt-Free Nickel Rich Layered Oxide Cathodes for Lithium-Ion Batteries
journal, October 2013

  • Sun, Yang-Kook; Lee, Dong-Ju; Lee, Yun Jung
  • ACS Applied Materials & Interfaces, Vol. 5, Issue 21
  • DOI: 10.1021/am403684z

Strategies for improving the cyclability and thermo-stability of LiMn 2 O 4 -based batteries at elevated temperatures
journal, January 2015

  • Xu, Gaojie; Liu, Zhihong; Zhang, Chuanjian
  • Journal of Materials Chemistry A, Vol. 3, Issue 8
  • DOI: 10.1039/C4TA06264G

Synthesis of full concentration gradient cathode studied by high energy X-ray diffraction
journal, January 2016

Effect of Cooling Rates on Phase Separation in 0.5Li 2 MnO 3 ·0.5LiCoO 2 Electrode Materials for Li-Ion Batteries
journal, May 2014

  • Long, Brandon R.; Croy, Jason R.; Dogan, Fulya
  • Chemistry of Materials, Vol. 26, Issue 11
  • DOI: 10.1021/cm501229t

Crystallization mechanism of LiNiO2 synthesized by Pechini method
journal, June 2001

Combinatorial Study of the Li–Ni–Mn–Co Oxide Pseudoquaternary System for Use in Li–Ion Battery Materials Research
journal, May 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

Template-Synthesized LiCoO 2 , LiMn 2 O 4 , and LiNi 0.8 Co 0.2 O 2 Nanotubes as the Cathode Materials of Lithium Ion Batteries
journal, July 2005

  • Li, Xiaoxia; Cheng, Fangyi; Guo, Bing
  • The Journal of Physical Chemistry B, Vol. 109, Issue 29
  • DOI: 10.1021/jp051900a

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

In situ x-ray diffraction and electrochemical studies of Li1−xNiO2
journal, December 1993

Minimization of the cation mixing in Li1+x(NMC)1−xO2 as cathode material
journal, March 2010

    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    Challenges in Developing Electrodes, Electrolytes, and Diagnostics Tools to Understand and Advance Sodium-Ion Batteries
    journal, February 2018

    • Xu, Gui-Liang; Amine, Rachid; Abouimrane, Ali
    • Advanced Energy Materials, Vol. 8, Issue 14
    • DOI: 10.1002/aenm.201702403

    Laser processed Ni-Fe alloys as electrocatalyst toward oxygen evolution reaction
    journal, June 2018

    • Cui, Xiaodan; Zhang, Boliang; Zeng, Congyuan
    • Materials Research Express, Vol. 5, Issue 6
    • DOI: 10.1088/2053-1591/aaca72

    Probing the Nature of Li + /Ni 2+ Disorder on the Structure and Electrochemical Performance in Ni-Based Layered Oxide Cathodes
    journal, January 2019

    • Zhang, Jicheng; Zhou, Dong; Yang, Wenyun
    • Journal of The Electrochemical Society, Vol. 166, Issue 16
    • DOI: 10.1149/2.0641916jes

    A Generalizable Top-Down Nanostructuring Method of Bulk Oxides: Sequential Oxygen-Nitrogen Exchange Reaction
    journal, May 2018

    Cooling Induced Surface Reconstruction during Synthesis of High‐Ni Layered Oxides
    journal, October 2019

    • Zhang, Ming‐Jian; Hu, Xiaobing; Li, Maofan
    • Advanced Energy Materials, Vol. 9, Issue 43
    • DOI: 10.1002/aenm.201901915

    Ti‐Gradient Doping to Stabilize Layered Surface Structure for High Performance High‐Ni Oxide Cathode of Li‐Ion Battery
    journal, September 2019

    • Kong, Defei; Hu, Jiangtao; Chen, Zhefeng
    • Advanced Energy Materials, Vol. 9, Issue 41
    • DOI: 10.1002/aenm.201901756

    High-voltage performance of concentration-gradient Li[Ni 0.6 Co 0.2 Mn 0.2 ]O 2 layered oxide cathode materials for lithium batteries
    journal, January 2018

    • Chen, Xianglei; Jia, Xiaobo; Qu, Yanyu
    • New Journal of Chemistry, Vol. 42, Issue 8
    • DOI: 10.1039/c7nj04936f

    Structure- and porosity-tunable, thermally reactive metal organic frameworks for high-performance Ni-rich layered oxide cathode materials with multi-scale pores
    journal, January 2019

    • Park, Jun-Ho; Park, Kwangjin; Han, Dongwook
    • Journal of Materials Chemistry A, Vol. 7, Issue 25
    • DOI: 10.1039/c9ta02462j

    Surface/Interface Structure Degradation of Ni‐Rich Layered Oxide Cathodes toward Lithium‐Ion Batteries: Fundamental Mechanisms and Remedying Strategies
    journal, December 2019

    • Liang, Longwei; Zhang, Wenheng; Zhao, Fei
    • Advanced Materials Interfaces, Vol. 7, Issue 3
    • DOI: 10.1002/admi.201901749

    Ultrathin Al2O3 Coating on LiNi0.8Co0.1Mn0.1O2 Cathode Material for Enhanced Cycleability at Extended Voltage Ranges
    journal, February 2019

    Theoretical investigation of the cation antisite defect in layer-structured cathode materials for Li-ion batteries
    journal, January 2019

    • Kim, Yongseon
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 43
    • DOI: 10.1039/c9cp05025f
      Sort by:
      [ × clear filter / sort ]

      Similar Records in DOE PAGES and OSTI.GOV collections: