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

Wangda Li; Xiaoming Liu; Hugo Celio; Patrick Smith; Andrei Dolocan; Miaofang Chi; Arumugam Manthiram

doi:10.1002/aenm.201703154

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

Wangda Li, Xiaoming Liu, Hugo Celio, Patrick Smith, Andrei Dolocan, Miaofang Chi, Arumugam Manthiram

electron Microscopy and Microanalysis

Research output: Contribution to journal › Article › peer-review

290 Scopus citations

Abstract

Nickel-rich layered oxide cathodes with the composition LiNi₁₋_x₋_yCo_xMn_yO₂ (NCM, (1−x−y) ≥ 0.6) are under intense scrutiny recently to contend with commercial LiNi_0.8Co_0.15Al_0.05O₂ (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_0.05O₂ and LiNi_0.7Co_0.15Mn_0.15O₂, 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.

Original language	English
Article number	1703154
Journal	Advanced Energy Materials
Volume	8
Issue number	15
DOIs	https://doi.org/10.1002/aenm.201703154
State	Published - May 25 2018

Funding

The authors gratefully acknowledge the support from the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the U.S. Department of Energy through the Advanced Battery Materials Research (BMR) Program (Battery 500 Consortium) award number DE-EE0007762 and the Welch Foundation F-1254. Electron microscopy work was supported by the U.S. DOE, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division (M.C., X.L.), and was conducted at the Center for Nanophase Materials Sciences, which is a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. The authors also thank Kristofer B. Ohlinger for assistance with the ion-milling equipment.

Funders	Funder number
DOE Office of Science
U.S. DOE
U.S. Department of Energy	DE-EE0007762
Welch Foundation	F-1254
Office of Science
Office of Energy Efficiency and Renewable Energy
Basic Energy Sciences
Oak Ridge National Laboratory
Vehicle Technologies Office
Division of Materials Sciences and Engineering

Keywords

aluminum and manganese substitution
electron microscopy
lithium-ion batteries
nickel-rich layered oxides
secondary-ion mass spectrometry

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1002/aenm.201703154

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title = "Mn versus Al in Layered Oxide Cathodes in Lithium-Ion Batteries: A Comprehensive Evaluation on Long-Term Cyclability",

abstract = "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.",

keywords = "aluminum and manganese substitution, electron microscopy, lithium-ion batteries, nickel-rich layered oxides, secondary-ion mass spectrometry",

author = "Wangda Li and Xiaoming Liu and Hugo Celio and Patrick Smith and Andrei Dolocan and Miaofang Chi and Arumugam Manthiram",

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AU - Smith, Patrick

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AB - 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.

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

Abstract

Funding

Keywords

UN SDGs

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