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Understanding and Mitigating the Dissolution and Delamination Issues Encountered with High-Voltage LiNi0.5Mn1.5O4

Journal Article · · Batteries
 [1];  [2];  [2];  [2];  [2];  [3];  [2];  [2];  [2];  [2]
  1. Argonne National Laboratory (ANL), Argonne, IL (United States); Univ. of Connecticut, Storrs, CT (United States)
  2. Argonne National Laboratory (ANL), Argonne, IL (United States)
  3. Univ. of Connecticut, Storrs, CT (United States)
+ Show Author Affiliations
In our initial study on the high-voltage 5 V cobalt-free spinel LiNi0.5Mn1.5O4 (LNMO) cathode, we discovered a severe delamination issue in the laminates when cycled at a high upper cut-off voltage (UCV) of 4.95 V, especially when a large cell format was used. This delamination problem prompted us to investigate further by studying the transition metal (TM) dissolution mechanism of cobalt-free LNMO cathodes, and as a comparison, some cobalt-containing lithium nickel manganese cobalt oxides (NMC) cathodes, as the leachates from the soaking experiment might be the culprit for the delamination. Unlike other previous reports, we are interested in the intrinsic stability of the cathode in the presence of a baseline Gen2 electrolyte consisting of 1.2 M of LiPF6 in ethylene carbonate/ethyl methyl carbonate (EC/EMC), similar to a storage condition. The electrode laminates (transition metal oxides, transition metal oxides, TMOs, coated on an Al current collector with a loading level of around 2.5 mAh/cm2) or the TMO powders (pure commercial quality spinel LNMO, NMC, etc.) were stored in the baseline solution, and the transition metal dissolution was studied through nuclear magnetic resonance, such as 1H NMR, 19F NMR, scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma mass spectrometry (ICP-MS). Significant electrolyte decomposition was observed and could be the cause that leads to the TM dissolution of LNMO. To address this TM dissolution, additives were introduced into the baseline electrolyte, effectively alleviating the issue of TM dissolution. The results suggest that the observed delamination is caused by electrolyte decompositions that lead to etching, and additives such as lithium difluorooxalato borate and p-toluenesulfonyl isocyanate can alleviate this issue by forming a firm cathode electrolyte interface. This study provides a new perspective on cell degradation induced by electrode/electrolyte interactions under storage conditions.
Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO); USDOE Office of Science (SC)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
2371038
Journal Information:
Batteries, Journal Name: Batteries Journal Issue: 9 Vol. 9; ISSN 2313-0105
Publisher:
MDPICopyright Statement
Country of Publication:
United States
Language:
English

References (16)

Surface and Subsurface Reactions of Lithium Transition Metal Oxide Cathode Materials: An Overview of the Fundamental Origins and Remedying Approaches journal September 2018
Enhancing the Electrochemical Performance of the LiMn2O4 Hollow Microsphere Cathode with a LiNi0.5Mn1.5O4 Coated Layer journal December 2013
Challenge in manufacturing electrolyte solutions for lithium and lithium ion batteries quality control and minimizing contamination level journal September 1999
Complexation of epigallocatechin gallate (a green tea extract, egcg) with Mn2+: nuclear spin relaxation by the paramagnetic ion journal February 2005
Structural underpinnings of cathode protection by in situ generated lithium oxyfluorophosphates journal October 2019
Quantifying Dissolved Transition Metals in Battery Electrolyte Solutions with NMR Paramagnetic Relaxation Enhancement journal May 2023
Dual-Salt Electrolytes to Effectively Reduce Impedance Rise of High-Nickel Lithium-Ion Batteries journal August 2021
Multifunctional Composite Binder for Thick High-Voltage Cathodes in Lithium-Ion Batteries journal December 2021
Electrolyte-Additive-Driven Interfacial Engineering for High-Capacity Electrodes in Lithium-Ion Batteries: Promise and Challenges journal April 2020
High-Voltage and High-Temperature LiCoO2 Operation via the Electrolyte Additive of Electron-Defect Boron Compounds journal May 2023
Electrode Degradation in Lithium-Ion Batteries journal January 2020
Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries journal October 2004
Mechanistic insights into lithium ion battery electrolyte degradation – a quantitative NMR study journal January 2016
High-voltage positive electrode materials for lithium-ion batteries journal January 2017
Developing high-voltage spinel LiNi 0.5 Mn 1.5 O 4 cathodes for high-energy-density lithium-ion batteries: current achievements and future prospects journal January 2020
Thermal Decomposition of LiPF[sub 6]-Based Electrolytes for Lithium-Ion Batteries journal January 2005

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Related Subjects

25 ENERGY STORAGE
LiNi0.5Mn1.5O4
additives
delamination
soaking
transition metal dissolutioon