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Title: Mn versus Al in Layered Oxide Cathodes in Lithium-Ion Batteries: A Comprehensive Evaluation on Long-Term Cyclability

Nickel-rich layered oxide cathodes with the composition LiNi 1-x-yCo xMn yO 2 (NCM, (1-x-y) ≥ 0.6) are under intense scrutiny recently to contend with commercial LiNi0.8Co0.15Al0.05O2 (NCA) for high-energy-density batteries for electric vehicles. However, a comprehensive assessment of their electrochemical durability is currently lacking. Herein, two in-house cathodes, LiNi 0.8Co 0.15Al 0.05O 2 and LiNi 0.7Co 0.15Mn 0.15O 2, are investigated in a high-voltage graphite full cell over 1500 charge-discharge cycles (≈5–10 year service life in vehicles). Despite a lower nickel content, NCM shows more performance deterioration than NCA. Critical underlying degradation processes, including chemical, structural, and mechanical aspects, are analyzed via an arsenal of characterization techniques. Overall, Mn substitution appears far less effective than Al in suppressing active mass dissolution and irreversible phase transitions of the layered oxide cathodes. The active mass dissolution (and crossover) accelerates capacity decline with sustained parasitic reactions on the graphite anode, while the phase transitions are primarily responsible for cell resistance increase and voltage fade. With Al doping, on the other hand, secondary particle pulverization is the more limiting factor for long-term cyclability compared to Mn. These results establish a fundamental guideline for designing high-performing Ni-rich NCM cathodes as a compelling alternative to NCAmore » and other compositions for electric vehicle applications.« less
Authors:
 [1] ;  [2] ;  [1] ;  [1] ;  [1] ;  [2] ; ORCiD logo [1]
  1. Univ. of Texas, Austin, TX (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Grant/Contract Number:
AC05-00OR22725; EE0007762
Type:
Accepted Manuscript
Journal Name:
Advanced Energy Materials
Additional Journal Information:
Journal Volume: 8; Journal Issue: 15; Journal ID: ISSN 1614-6832
Publisher:
Wiley
Research Org:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE
OSTI Identifier:
1470844
Alternate Identifier(s):
OSTI ID: 1419355

Li, Wangda, Liu, Xiaoming, Celio, Hugo, Smith, Patrick, Dolocan, Andrei, Chi, Miaofang, and Manthiram, Arumugam. Mn versus Al in Layered Oxide Cathodes in Lithium-Ion Batteries: A Comprehensive Evaluation on Long-Term Cyclability. United States: N. p., Web. doi:10.1002/aenm.201703154.
Li, Wangda, Liu, Xiaoming, Celio, Hugo, Smith, Patrick, Dolocan, Andrei, Chi, Miaofang, & Manthiram, Arumugam. Mn versus Al in Layered Oxide Cathodes in Lithium-Ion Batteries: A Comprehensive Evaluation on Long-Term Cyclability. United States. doi:10.1002/aenm.201703154.
Li, Wangda, Liu, Xiaoming, Celio, Hugo, Smith, Patrick, Dolocan, Andrei, Chi, Miaofang, and Manthiram, Arumugam. 2018. "Mn versus Al in Layered Oxide Cathodes in Lithium-Ion Batteries: A Comprehensive Evaluation on Long-Term Cyclability". United States. doi:10.1002/aenm.201703154.
@article{osti_1470844,
title = {Mn versus Al in Layered Oxide Cathodes in Lithium-Ion Batteries: A Comprehensive Evaluation on Long-Term Cyclability},
author = {Li, Wangda and Liu, Xiaoming and Celio, Hugo and Smith, Patrick and Dolocan, Andrei and Chi, Miaofang and Manthiram, Arumugam},
abstractNote = {Nickel-rich layered oxide cathodes with the composition LiNi1-x-yCoxMnyO2 (NCM, (1-x-y) ≥ 0.6) are under intense scrutiny recently to contend with commercial LiNi0.8Co0.15Al0.05O2 (NCA) for high-energy-density batteries for electric vehicles. However, a comprehensive assessment of their electrochemical durability is currently lacking. Herein, two in-house cathodes, LiNi0.8Co0.15Al0.05O2 and LiNi0.7Co0.15Mn0.15O2, are investigated in a high-voltage graphite full cell over 1500 charge-discharge cycles (≈5–10 year service life in vehicles). Despite a lower nickel content, NCM shows more performance deterioration than NCA. Critical underlying degradation processes, including chemical, structural, and mechanical aspects, are analyzed via an arsenal of characterization techniques. Overall, Mn substitution appears far less effective than Al in suppressing active mass dissolution and irreversible phase transitions of the layered oxide cathodes. The active mass dissolution (and crossover) accelerates capacity decline with sustained parasitic reactions on the graphite anode, while the phase transitions are primarily responsible for cell resistance increase and voltage fade. With Al doping, on the other hand, secondary particle pulverization is the more limiting factor for long-term cyclability compared to Mn. These results establish a fundamental guideline for designing high-performing Ni-rich NCM cathodes as a compelling alternative to NCA and other compositions for electric vehicle applications.},
doi = {10.1002/aenm.201703154},
journal = {Advanced Energy Materials},
number = 15,
volume = 8,
place = {United States},
year = {2018},
month = {2}
}