Synthetic Control of Kinetic Reaction Pathway and Cationic Ordering in High-Ni Layered Oxide Cathodes
Abstract
Nickel-rich layered transition metal oxides, LiNi1-x(MnCo)(x)O-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 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.
- Authors:
-
- Brookhaven National Lab. (BNL), Upton, NY (United States); Xiamen Univ. (China)
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Brookhaven National Lab. (BNL), Upton, NY (United States); Peking Univ. Shenzhen Graduate School (China)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Cornell Univ., Ithaca, NY (United States)
- Peking Univ. Shenzhen Graduate School (China)
- Hayang Univ., Seoul (Korea, Republic of)
- Xiamen Univ. (China)
- Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
- Publication Date:
- Research Org.:
- Brookhaven National Laboratory (BNL), Upton, NY (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); USDOE
- 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; DE‐SC0012704; DE‐AC02‐06CH11357; AC05-00OR22725; AC02-06CH11357
- Resource Type:
- Journal Article: 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. https://doi.org/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. 2017.
"Synthetic Control of Kinetic Reaction Pathway and Cationic Ordering in High-Ni Layered Oxide Cathodes". United States. https://doi.org/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)(x)O-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 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},
url = {https://www.osti.gov/biblio/1389227},
journal = {Advanced Materials},
issn = {0935-9648},
number = 39,
volume = 29,
place = {United States},
year = {Fri Aug 25 00:00:00 EDT 2017},
month = {Fri Aug 25 00:00:00 EDT 2017}
}
Web of Science
Works referenced in this record:
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
Electrochemical Reaction of Lithium with Nanostructured Silicon Anodes: A Study by In-Situ Synchrotron X-Ray Diffraction and Electron Energy-Loss Spectroscopy
journal, August 2013
- Wang, Feng; Wu, Lijun; Key, Baris
- Advanced Energy Materials, Vol. 3, Issue 10
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
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
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
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
- Kim, Hyoung-Geun; Myung, Seung-Taek; Lee, Jung Kyu
- Journal of Power Sources, Vol. 196, Issue 16
Unlocking the Potential of Cation-Disordered Oxides for Rechargeable Lithium Batteries
journal, January 2014
- Lee, J.; Urban, A.; Li, X.
- Science, Vol. 343, Issue 6170
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
Optimized Temperature Effect of Li-Ion Diffusion with Layer Distance in Li(Ni x Mn y Co z )O 2 Cathode Materials for High Performance Li-Ion Battery
journal, December 2015
- Cui, Suihan; Wei, Yi; Liu, Tongchao
- Advanced Energy Materials, Vol. 6, Issue 4
Nanostructured Black Phosphorus/Ketjenblack–Multiwalled Carbon Nanotubes Composite as High Performance Anode Material for Sodium-Ion Batteries
journal, May 2016
- Xu, Gui-Liang; Chen, Zonghai; Zhong, Gui-Ming
- Nano Letters, Vol. 16, Issue 6
Aligned Li + Tunnels in Core–Shell Li(Ni x Mn y Co z )O 2 @LiFePO 4 Enhances Its High Voltage Cycling Stability as Li-ion Battery Cathode
journal, September 2016
- Wu, Zhongzhen; Ji, Shunping; Liu, Tongchao
- Nano Letters, Vol. 16, Issue 10
Improved cycle stability and high-rate capability of Li3VO4-coated Li[Ni0.5Co0.2Mn0.3]O2 cathode material under different voltages
journal, June 2014
- Huang, Yan; Jin, Feng-Min; Chen, Fang-Jie
- Journal of Power Sources, Vol. 256
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
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
Ultimate Limits to Intercalation Reactions for Lithium Batteries
journal, October 2014
- Whittingham, M. Stanley
- Chemical Reviews, Vol. 114, Issue 23
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
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
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
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
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
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
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
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
Prelithiation Activates Li(Ni 0.5 Mn 0.3 Co 0.2 )O 2 for High Capacity and Excellent Cycling Stability
journal, July 2015
- Wu, Zhongzhen; Ji, Shunping; Zheng, Jiaxin
- Nano Letters, Vol. 15, Issue 8
Improvement of electrochemical and thermal properties of Li[Ni0.8Co0.1Mn0.1]O2 positive electrode materials by multiple metal (Al, Mg) substitution
journal, June 2009
- Woo, S. -W.; Myung, S. -T.; Bang, H.
- Electrochimica Acta, Vol. 54, Issue 15
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
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
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
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
Effect of cobalt substitution on cationic distribution in LiNi1 − y CoyO2 electrode materials
journal, September 1996
- Rougier, A.
- Solid State Ionics, Vol. 90, Issue 1-4
Factors that affect Li mobility in layered lithium transition metal oxides
journal, September 2006
- Kang, Kisuk; Ceder, Gerbrand
- Physical Review B, Vol. 74, Issue 9
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
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
Combining In Situ Synchrotron X-Ray Diffraction and Absorption Techniques with Transmission Electron Microscopy to Study the Origin of Thermal Instability in Overcharged Cathode Materials for Lithium-Ion Batteries
journal, June 2012
- Nam, Kyung-Wan; Bak, Seong-Min; Hu, Enyuan
- Advanced Functional Materials, Vol. 23, Issue 8
Synthesis of full concentration gradient cathode studied by high energy X-ray diffraction
journal, January 2016
- Li, Yan; Xu, Rui; Ren, Yang
- Nano Energy, Vol. 19
A Size-Dependent Sodium Storage Mechanism in Li 4 Ti 5 O 12 Investigated by a Novel Characterization Technique Combining in Situ X-ray Diffraction and Chemical Sodiation
journal, September 2013
- Yu, Xiqian; Pan, Huilin; Wan, Wang
- Nano Letters, Vol. 13, Issue 10
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
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
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
The role of nanotechnology in the development of battery materials for electric vehicles
journal, December 2016
- Lu, Jun; Chen, Zonghai; Ma, Zifeng
- Nature Nanotechnology, Vol. 11, Issue 12
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
A perspective on nickel-rich layered oxide cathodes for lithium-ion batteries
journal, January 2017
- Manthiram, Arumugam; Song, Bohang; Li, Wangda
- Energy Storage Materials, Vol. 6
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
An approach to application for LiNi0.6Co0.2Mn0.2O2 cathode material at high cutoff voltage by TiO2 coating
journal, June 2014
- Chen, Yanping; Zhang, Yun; Chen, Baojun
- Journal of Power Sources, Vol. 256
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
Ameliorating the Interfacial Problems of Cathode and Solid‐State Electrolytes by Interface Modification of Functional Polymers
journal, July 2018
- Wang, Li‐Ping; Zhang, Xu‐Dong; Wang, Tai‐Shan
- Advanced Energy Materials, Vol. 8, Issue 24
Microstructure Evolution of Concentration Gradient Li[Ni 0.75 Co 0.10 Mn 0.15 ]O 2 Cathode for Lithium-Ion Batteries
journal, May 2018
- Yoon, Chong S.; Kim, Suk Jun; Kim, Un-Hyuck
- Advanced Functional Materials, Vol. 28, Issue 28
Trace doping of multiple elements enables stable battery cycling of LiCoO2 at 4.6 V
journal, June 2019
- Zhang, Jie-Nan; Li, Qinghao; Ouyang, Chuying
- Nature Energy, Vol. 4, Issue 7
Influence of Calcination Temperature on Structure and Electrochemical Behavior of LiNi0.83 Co0.11Mn0.06O2 Cathodes for Lithium-Ion Batteries
journal, January 2019
- Wang, Jing; Li, Dan Hua; Wang, Ran
- Materials Science Forum, Vol. 944
Use of Ce to Reinforce the Interface of Ni-Rich LiNi 0.8 Co 0.1 Mn 0.1 O 2 Cathode Materials for Lithium-Ion Batteries under High Operating Voltage
journal, January 2019
- Wu, Feng; Li, Qing; Chen, Lai
- ChemSusChem, Vol. 12, Issue 4
Identifying the Origin and Contribution of Surface Storage in TiO 2 (B) Nanotube Electrode by In Situ Dynamic Valence State Monitoring
journal, July 2018
- Tang, Yuxin; Zhang, Yanyan; Malyi, Oleksandr I.
- Advanced Materials, Vol. 30, Issue 33
Self-assembly of polyoxometalate/reduced graphene oxide composites induced by ionic liquids as a high-rate cathode for batteries: “killing two birds with one stone”
journal, January 2018
- Shen, Feng-Cui; Wang, Yi-Rong; Li, Shun-Li
- Journal of Materials Chemistry A, Vol. 6, Issue 4
Investigating the Effects of Magnesium Doping in Various Ni-Rich Positive Electrode Materials for Lithium Ion Batteries
journal, January 2019
- Liu, Aaron; Zhang, Ning; Li, Hongyang
- Journal of The Electrochemical Society, Vol. 166, Issue 16
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
Increase and discretization of the energy barrier for individual LiNi x Co y Mn y O 2 ( x + 2 y =1) particles with the growth of a Li 2 CO 3 surface film
journal, January 2019
- Qian, Kun; Huang, Binhua; Liu, Yuxiu
- Journal of Materials Chemistry A, Vol. 7, Issue 20
ZnNi x Mn x Co 2-2 x O 4 Spinel as a High-Voltage and High-Capacity Cathode Material for Nonaqueous Zn-Ion Batteries
journal, May 2018
- Pan, Chengsi; Zhang, Ruixian; Nuzzo, Ralph G.
- Advanced Energy Materials, Vol. 8, Issue 22