skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Synthetic Control of Kinetic Reaction Pathway and Cationic Ordering in High-Ni Layered Oxide Cathodes

Abstract

Nickel-rich layered transition metal oxides, LiNi 1-x(MnCo) xO 2 (1-x ≥ 0.5), are appealing candidates for cathodes in next-generation lithium-ion batteries (LIBs) for electric vehicles and other large-scale applications, due to their high capacity and low cost. However, synthetic control of the structural ordering in such a complex quaternary system has been a great challenge, especially in the presence of high Ni content. Herein, synthesis reactions for preparing layered LiNi 0.7Mn 0.15Co 0.15O 2 (NMC71515) by solid-state methods are investigated through a combination of time-resolved in situ high-energy X-ray diffraction and absorption spectroscopy measurements. The real-time observation reveals a strong temperature dependence of the kinetics of cationic ordering in NMC71515 as a result of thermal-driven oxidation of transition metals and lithium/oxygen loss that concomitantly occur during heat treatment. Through synthetic control of the kinetic reaction pathway, a layered NMC71515 with low cationic disordering and a high reversible capacity is prepared in air. The findings may help to pave the way for designing high-Ni layered oxide cathodes for LIBs

Authors:
 [1];  [2];  [2];  [2];  [3];  [4];  [2];  [5];  [6];  [7];  [8];  [9];  [2];  [10];  [2]; ORCiD logo [3]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States); Xiamen Univ. (China)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
  4. Brookhaven National Lab. (BNL), Upton, NY (United States); Peking Univ. Shenzhen Graduate School (China)
  5. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  6. Cornell Univ., Ithaca, NY (United States)
  7. Peking Univ. Shenzhen Graduate School (China)
  8. Hayang Univ., Seoul (Korea, Republic of)
  9. Xiamen Univ. (China)
  10. Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1389227
Alternate Identifier(s):
OSTI ID: 1376967; OSTI ID: 1414679; OSTI ID: 1422578
Report Number(s):
BNL-114143-2017-JA
Journal ID: ISSN 0935-9648
Grant/Contract Number:  
SC0012704; AC02-06CH11357; AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Materials
Additional Journal Information:
Journal Volume: 29; Journal Issue: 39; Journal ID: ISSN 0935-9648
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Wang, Dawei, Kou, Ronghui, Ren, Yang, Sun, Cheng-Jun, Zhao, Hu, Zhang, Ming-Jian, Li, Yan, Huq, Ashifia, Ko, J. Y. Peter, Pan, Feng, Sun, Yang-Kook, Yang, Yong, Amine, Khalil, Bai, Jianming, Chen, Zonghai, and Wang, Feng. Synthetic Control of Kinetic Reaction Pathway and Cationic Ordering in High-Ni Layered Oxide Cathodes. United States: N. p., 2017. Web. doi:10.1002/adma.201606715.
Wang, Dawei, Kou, Ronghui, Ren, Yang, Sun, Cheng-Jun, Zhao, Hu, Zhang, Ming-Jian, Li, Yan, Huq, Ashifia, Ko, J. Y. Peter, Pan, Feng, Sun, Yang-Kook, Yang, Yong, Amine, Khalil, Bai, Jianming, Chen, Zonghai, & Wang, Feng. Synthetic Control of Kinetic Reaction Pathway and Cationic Ordering in High-Ni Layered Oxide Cathodes. United States. doi:10.1002/adma.201606715.
Wang, Dawei, Kou, Ronghui, Ren, Yang, Sun, Cheng-Jun, Zhao, Hu, Zhang, Ming-Jian, Li, Yan, Huq, Ashifia, Ko, J. Y. Peter, Pan, Feng, Sun, Yang-Kook, Yang, Yong, Amine, Khalil, Bai, Jianming, Chen, Zonghai, and Wang, Feng. Fri . "Synthetic Control of Kinetic Reaction Pathway and Cationic Ordering in High-Ni Layered Oxide Cathodes". United States. doi:10.1002/adma.201606715. https://www.osti.gov/servlets/purl/1389227.
@article{osti_1389227,
title = {Synthetic Control of Kinetic Reaction Pathway and Cationic Ordering in High-Ni Layered Oxide Cathodes},
author = {Wang, Dawei and Kou, Ronghui and Ren, Yang and Sun, Cheng-Jun and Zhao, Hu and Zhang, Ming-Jian and Li, Yan and Huq, Ashifia and Ko, J. Y. Peter and Pan, Feng and Sun, Yang-Kook and Yang, Yong and Amine, Khalil and Bai, Jianming and Chen, Zonghai and Wang, Feng},
abstractNote = {Nickel-rich layered transition metal oxides, LiNi1-x(MnCo)xO2 (1-x ≥ 0.5), are appealing candidates for cathodes in next-generation lithium-ion batteries (LIBs) for electric vehicles and other large-scale applications, due to their high capacity and low cost. However, synthetic control of the structural ordering in such a complex quaternary system has been a great challenge, especially in the presence of high Ni content. Herein, synthesis reactions for preparing layered LiNi0.7Mn0.15Co0.15O2 (NMC71515) by solid-state methods are investigated through a combination of time-resolved in situ high-energy X-ray diffraction and absorption spectroscopy measurements. The real-time observation reveals a strong temperature dependence of the kinetics of cationic ordering in NMC71515 as a result of thermal-driven oxidation of transition metals and lithium/oxygen loss that concomitantly occur during heat treatment. Through synthetic control of the kinetic reaction pathway, a layered NMC71515 with low cationic disordering and a high reversible capacity is prepared in air. The findings may help to pave the way for designing high-Ni layered oxide cathodes for LIBs},
doi = {10.1002/adma.201606715},
journal = {Advanced Materials},
number = 39,
volume = 29,
place = {United States},
year = {2017},
month = {8}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 15 works
Citation information provided by
Web of Science

Save / Share:

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

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

Charge, Potential, and Phase Stability of Layered Li(Ni[sub 0.5]Mn[sub 0.5])O[sub 2]
journal, January 2002

  • Reed, J.; Ceder, G.
  • Electrochemical and Solid-State Letters, Vol. 5, Issue 7
  • DOI: 10.1149/1.1480135

Improvement of Electrochemical Performances of Li[Ni[sub 0.8]Co[sub 0.1]Mn[sub 0.1]]O[sub 2] Cathode Materials by Fluorine Substitution
journal, January 2007

  • Woo, S. -U.; Park, B. -C.; Yoon, C. S.
  • Journal of The Electrochemical Society, Vol. 154, Issue 7
  • DOI: 10.1149/1.2735916

Advanced Concentration Gradient Cathode Material with Two-Slope for High-Energy and Safe Lithium Batteries
journal, June 2015

  • Lim, Byung-Beom; Yoon, Sung-Jun; Park, Kang-Joon
  • Advanced Functional Materials, Vol. 25, Issue 29
  • DOI: 10.1002/adfm.201501430

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

Experimental and First-Principles Thermodynamic Study of the Formation and Effects of Vacancies in Layered Lithium Nickel Cobalt Oxides
journal, December 2011

  • Kim, Yongseon; Kim, Doyu; Kang, Shinhoo
  • Chemistry of Materials, Vol. 23, Issue 24
  • DOI: 10.1021/cm202415x

Structural and Electrochemical Properties of Layered Li[Ni[sub 1−2x]Co[sub x]Mn[sub x]]O[sub 2] (x=0.1–0.3) Positive Electrode Materials for Li-Ion Batteries
journal, January 2007

  • Lee, K. -S.; Myung, S. -T.; Amine, K.
  • Journal of The Electrochemical Society, Vol. 154, Issue 10
  • DOI: 10.1149/1.2769831

In Situ Probing and Synthetic Control of Cationic Ordering in Ni-Rich Layered Oxide Cathodes
journal, October 2016

  • Zhao, Jianqing; Zhang, Wei; Huq, Ashfia
  • Advanced Energy Materials, Vol. 7, Issue 3
  • DOI: 10.1002/aenm.201601266

Prelithiation Activates Li(Ni 0.5 Mn 0.3 Co 0.2 )O 2 for High Capacity and Excellent Cycling Stability
journal, July 2015


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

Synthesis and Characterization of Li[(Ni 0.8 Co 0.1 Mn 0.1 ) 0.8 (Ni 0.5 Mn 0.5 ) 0.2 ]O 2 with the Microscale Core−Shell Structure as the Positive Electrode Material for Lithium Batteries
journal, September 2005

  • Sun, Yang-Kook; Myung, Seung-Taek; Kim, Myung-Hoon
  • Journal of the American Chemical Society, Vol. 127, Issue 38
  • DOI: 10.1021/ja053675g

High-energy x-ray scattering studies of battery materials
journal, June 2016

  • Glazer, Matthew P. B.; Okasinski, John S.; Almer, Jonathan D.
  • MRS Bulletin, Vol. 41, Issue 6
  • DOI: 10.1557/mrs.2016.96

Effects of manganese and cobalt on the electrochemical and thermal properties of layered Li[Ni0.52Co0.16+xMn0.32−x]O2 cathode materials
journal, August 2011


High-Energy Layered Oxide Cathodes with Thin Shells for Improved Surface Stability
journal, October 2014

  • Noh, Hyung-Joo; Myung, Seung-Taek; Lee, Yun Jung
  • Chemistry of Materials, Vol. 26, Issue 20
  • DOI: 10.1021/cm502774u

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


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


Lithium Diffusion in Layered Li[sub x]CoO[sub 2]
journal, January 1999

  • Van der Ven, A.
  • Electrochemical and Solid-State Letters, Vol. 3, Issue 7
  • DOI: 10.1149/1.1391130

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


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

Role of Electronic Structure in the Susceptibility of Metastable Transition-Metal Oxide Structures to Transformation
journal, October 2004

  • Reed, John; Ceder, Gerbrand
  • Chemical Reviews, Vol. 104, Issue 10
  • DOI: 10.1021/cr020733x

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


High-energy cathode material for long-life and safe lithium batteries
journal, March 2009

  • Sun, Yang-Kook; Myung, Seung-Taek; Park, Byung-Chun
  • Nature Materials, Vol. 8, Issue 4
  • DOI: 10.1038/nmat2418

Progress in High-Capacity Core–Shell Cathode Materials for Rechargeable Lithium Batteries
journal, January 2014

  • Myung, Seung-Taek; Noh, Hyung-Joo; Yoon, Sung-June
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 4
  • DOI: 10.1021/jz402691z

Microstructural Changes in LiNi0.8Co0.15Al0.05O2 Positive Electrode Material during the First Cycle
journal, January 2011

  • Zheng, Shijian; Huang, Rong; Makimura, Yoshinari
  • Journal of The Electrochemical Society, Vol. 158, Issue 4
  • DOI: 10.1149/1.3544843

The role of nanotechnology in the development of battery materials for electric vehicles
journal, December 2016


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

Local Structure and Cation Ordering in O3 Lithium Nickel Manganese Oxides with Stoichiometry Li[Ni[sub x]Mn[sub (2−x)/3]Li[sub (1−2x)/3]]O[sub 2]
journal, January 2004

  • Yoon, Won-Sub; Iannopollo, Steven; Grey, Clare P.
  • Electrochemical and Solid-State Letters, Vol. 7, Issue 7
  • DOI: 10.1149/1.1737711

A new in situ synchrotron X-ray diffraction technique to study the chemical delithiation of LiFePO4
journal, January 2011

  • Wang, Xiao-Jian; Chen, Hai-Yan; Yu, Xiqian
  • Chemical Communications, Vol. 47, Issue 25
  • DOI: 10.1039/c1cc10870k

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

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

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


Improved Performances of Li[Ni 0.65 Co 0.08 Mn 0.27 ]O 2 Cathode Material with Full Concentration Gradient for Li-Ion Batteries
journal, December 2014

  • Yoon, Sung-Jun; Park, Kang-Joon; Lim, Byung-Beom
  • Journal of The Electrochemical Society, Vol. 162, Issue 2
  • DOI: 10.1149/2.0101502jes

Solid state synthesis of LiFePO4 studied by in situ high energy X-ray diffraction
journal, January 2011

  • Chen, Zonghai; Ren, Yang; Qin, Yan
  • Journal of Materials Chemistry, Vol. 21, Issue 15
  • DOI: 10.1039/c0jm04049e

An approach to application for LiNi0.6Co0.2Mn0.2O2 cathode material at high cutoff voltage by TiO2 coating
journal, June 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