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

Journal Article · · Advanced Energy Materials
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  1. Univ. of Texas, Austin, TX (United States)
  2. Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
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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. Finally, 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.

Research Organization:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
1470844
Alternate ID(s):
OSTI ID: 1419355
OSTI ID: 2217318
Journal Information:
Advanced Energy Materials, Journal Name: Advanced Energy Materials Journal Issue: 15 Vol. 8; ISSN 1614-6832
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English

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A General One‐Pot Synthesis Strategy of 3D Porous Hierarchical Networks Crosslinked by Monolayered Nanoparticles Interconnected Nanoplates for Lithium Ion Batteries journal June 2019
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Investigation of Interfacial Changes on Grain Boundaries of Li(Ni 0.5 Co 0.2 Mn 0.3 )O 2 in the Initial Overcharge Process journal February 2019
Surface/Interface Structure Degradation of Ni‐Rich Layered Oxide Cathodes toward Lithium‐Ion Batteries: Fundamental Mechanisms and Remedying Strategies journal December 2019
Extending the Service Life of High-Ni Layered Oxides by Tuning the Electrode-Electrolyte Interphase journal September 2018
Kinetic Stability of Bulk LiNiO 2 and Surface Degradation by Oxygen Evolution in LiNiO 2 -Based Cathode Materials journal November 2018
Oxygen Release Degradation in Li‐Ion Battery Cathode Materials: Mechanisms and Mitigating Approaches journal April 2019
Ethylene Carbonate‐Free Electrolytes for High‐Nickel Layered Oxide Cathodes in Lithium‐Ion Batteries journal June 2019
A Low‐Cost Durable Na‐FeCl 2 Battery with Ultrahigh Rate Capability journal March 2020
In‐Depth TEM Investigation on Structural Inhomogeneity within a Primary Li x Ni 0.835 Co 0.15 Al 0.015 O 2 Particle: Origin of Capacity Decay during High‐Rate Discharge journal November 2019
In‐Depth TEM Investigation on Structural Inhomogeneity within a Primary Li x Ni 0.835 Co 0.15 Al 0.015 O 2 Particle: Origin of Capacity Decay during High‐Rate Discharge journal February 2020
Lattice doping regulated interfacial reactions in cathode for enhanced cycling stability journal August 2019
High-nickel layered oxide cathodes for lithium-based automotive batteries journal January 2020
MoS 2 nanosheets with expanded interlayer spacing for enhanced sodium storage journal January 2018
Self-standing Li 1.2 Mn 0.6 Ni 0.2 O 2 /graphene membrane as a binder-free cathode for Li-ion batteries journal January 2018
Stabilizing nickel-rich layered oxide cathodes by magnesium doping for rechargeable lithium-ion batteries journal January 2019
An environment-friendly approach to produce nanostructured germanium anodes for lithium-ion batteries journal January 2020
Structure and electrochemical performance modulation of a LiNi 0.8 Co 0.1 Mn 0.1 O 2 cathode material by anion and cation co-doping for lithium ion batteries journal January 2019
Advanced cathode materials and efficient electrolytes for rechargeable batteries: practical challenges and future perspectives journal January 2019
LiFePO 4 -Coated LiNi 0.5 Co 0.2 Mn 0.3 O 2 Cathode Materials with Improved High Voltage Electrochemical Performance and Enhanced Safety for Lithium Ion Pouch Cells journal January 2019
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