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Title: Tuning of Thermal Stability in Layered Li(Ni x Mn y Co z )O 2

Abstract

Understanding and further designing new layered Li(Ni xMn yCo z)O 2 (NMC) (x + y + z = 1) materials with optimized thermal stability is important to rechargeable Li batteries (LIBs) for electrical vehicles (EV). Using ab initio calculations combined with experiments, we clarified how the thermal stability of NMC materials can be tuned by the most unstable oxygen, which is determined by the local coordination structure unit (LCSU) of oxygen (TM(Ni, Mn, Co) 3-O-Li 3-x'): each O atom bonds with three transition metals (TM) from the TM-layer and three to zero Li from fully discharged to charged states from the Li-layer. Under this model, how the lithium content, valence states of Ni, contents of Ni, Mn, and Co, and Ni/Li disorder to tune the thermal stability of NMC materials by affecting the sites, content, and the release temperature of the most unstable oxygen is proposed. The synergistic effect between Li vacancies and raised valence state of Ni during delithiation process can aggravate instability of oxygen, and oxygen coordinated with more nickel (especially with high valence state) in LSCU becomes more unstable at a fixed delithiation state. The Ni/Li mixing would decrease the thermal stability of the “NiMn” group NMCmore » materials but benefit the thermal stability of “Ni-rich” group, because the Ni in the Li layer would form 180° Ni-O-Ni super exchange chains in “Ni-rich” NMC materials. Mn and Co doping can tune the initial valence state of Ni, local coordination environment of oxygen, and the Ni/Li disorder, thus to tune the thermal stability directly.« less

Authors:
; ; ; ; ; ; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1340886
Report Number(s):
PNNL-SA-122525
Journal ID: ISSN 0002-7863; 48379; KP1704020
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of the American Chemical Society; Journal Volume: 138; Journal Issue: 40
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; Environmental Molecular Sciences Laboratory

Citation Formats

Zheng, Jiaxin, Liu, Tongchao, Hu, Zongxiang, Wei, Yi, Song, Xiaohe, Ren, Yang, Wang, Weidong, Rao, Mumin, Lin, Yuan, Chen, Zonghai, Lu, Jun, Wang, Chongmin, Amine, Khalil, and Pan, Feng. Tuning of Thermal Stability in Layered Li(Ni x Mn y Co z )O 2. United States: N. p., 2016. Web. doi:10.1021/jacs.6b07771.
Zheng, Jiaxin, Liu, Tongchao, Hu, Zongxiang, Wei, Yi, Song, Xiaohe, Ren, Yang, Wang, Weidong, Rao, Mumin, Lin, Yuan, Chen, Zonghai, Lu, Jun, Wang, Chongmin, Amine, Khalil, & Pan, Feng. Tuning of Thermal Stability in Layered Li(Ni x Mn y Co z )O 2. United States. doi:10.1021/jacs.6b07771.
Zheng, Jiaxin, Liu, Tongchao, Hu, Zongxiang, Wei, Yi, Song, Xiaohe, Ren, Yang, Wang, Weidong, Rao, Mumin, Lin, Yuan, Chen, Zonghai, Lu, Jun, Wang, Chongmin, Amine, Khalil, and Pan, Feng. Mon . "Tuning of Thermal Stability in Layered Li(Ni x Mn y Co z )O 2". United States. doi:10.1021/jacs.6b07771.
@article{osti_1340886,
title = {Tuning of Thermal Stability in Layered Li(Ni x Mn y Co z )O 2},
author = {Zheng, Jiaxin and Liu, Tongchao and Hu, Zongxiang and Wei, Yi and Song, Xiaohe and Ren, Yang and Wang, Weidong and Rao, Mumin and Lin, Yuan and Chen, Zonghai and Lu, Jun and Wang, Chongmin and Amine, Khalil and Pan, Feng},
abstractNote = {Understanding and further designing new layered Li(NixMnyCoz)O2 (NMC) (x + y + z = 1) materials with optimized thermal stability is important to rechargeable Li batteries (LIBs) for electrical vehicles (EV). Using ab initio calculations combined with experiments, we clarified how the thermal stability of NMC materials can be tuned by the most unstable oxygen, which is determined by the local coordination structure unit (LCSU) of oxygen (TM(Ni, Mn, Co)3-O-Li3-x'): each O atom bonds with three transition metals (TM) from the TM-layer and three to zero Li from fully discharged to charged states from the Li-layer. Under this model, how the lithium content, valence states of Ni, contents of Ni, Mn, and Co, and Ni/Li disorder to tune the thermal stability of NMC materials by affecting the sites, content, and the release temperature of the most unstable oxygen is proposed. The synergistic effect between Li vacancies and raised valence state of Ni during delithiation process can aggravate instability of oxygen, and oxygen coordinated with more nickel (especially with high valence state) in LSCU becomes more unstable at a fixed delithiation state. The Ni/Li mixing would decrease the thermal stability of the “NiMn” group NMC materials but benefit the thermal stability of “Ni-rich” group, because the Ni in the Li layer would form 180° Ni-O-Ni super exchange chains in “Ni-rich” NMC materials. Mn and Co doping can tune the initial valence state of Ni, local coordination environment of oxygen, and the Ni/Li disorder, thus to tune the thermal stability directly.},
doi = {10.1021/jacs.6b07771},
journal = {Journal of the American Chemical Society},
number = 40,
volume = 138,
place = {United States},
year = {Mon Sep 19 00:00:00 EDT 2016},
month = {Mon Sep 19 00:00:00 EDT 2016}
}