Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Revisiting the Mechanism Behind Transition-Metal Dissolution from Delithiated LiNixMnyCozO2 (NMC) Cathodes

Journal Article · · Journal of the Electrochemical Society (Online)
 [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1]
  1. Argonne National Lab. (ANL), Lemont, IL (United States)
+ Show Author Affiliations

Dissolution of transition metals (TMs) from lithium-ion battery cathodes under high-voltage conditions is a major issue affecting battery performance that is not well understood mechanistically. Here, this phenomenon is studied by chemically aging pristine and charged LiNi0.5Mn0.3Co0.2O2 (NMC532) cathodes in the presence of different solutions. The solution composition was varied by 1) adding water to a standard electrolyte, 2) replacing LiPF6 salt with lithium acetylacetonate (Li-acac), 3) and/or adding oxidatively unstable tris(2,2,2-trifluoroethyl) phosphite (TTFP) as an electrolyte additive. Our results demonstrate that while TM dissolution from pristine NMC532 cathodes is dominated by HF-attack, TM dissolution from charged NMC532 cathodes is affected by many other factors apart from HF-attack. We suggest that reduction of TMs due to chemical/electrochemical oxidation of the electrolyte at cathode/electrolyte interface, followed by formation of soluble TM-complexes with concomitant Li+ intercalation into the cathode, is the dominant mechanism of TM-dissolution at high voltage.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1607632
Journal Information:
Journal of the Electrochemical Society (Online), Vol. 167, Issue 2; ISSN 1945-7111
Publisher:
IOP PublishingCopyright Statement
Country of Publication:
United States
Language:
English

References (44)

Effects of Dissolved Transition Metals on the Electrochemical Performance and SEI Growth in Lithium-Ion Batteries journal January 2014
Stability of Lithium Ion Spinel Cells. III. Improved Life of Charged Cells journal January 2000
Generalized Gradient Approximation Made Simple journal October 1996
Improved capacity retention in rechargeable 4 V lithium/lithium-manganese oxide (spinel) cells journal April 1994
The influence of different conducting salts on the metal dissolution and capacity fading of NCM cathode material journal July 2014
Tris(trimethylsilyl)borate as an electrolyte additive for improving interfacial stability of high voltage layered lithium-rich oxide cathode/carbonate-based electrolyte journal July 2015
Reaction Energy for LiMn[sub 2]O[sub 4] Spinel Dissolution in Acid journal January 2006
Dissolution of Spinel Oxides and Capacity Losses in 4V Li / LixMn2O4 Cells journal January 1996
First-Principles Analysis of Phase Stability in Layered–Layered Composite Cathodes for Lithium-Ion Batteries journal March 2014
Why is tris(trimethylsilyl) phosphite effective as an additive for high-voltage lithium-ion batteries? journal January 2015
Steric effects of phosphorus ligands in organometallic chemistry and homogeneous catalysis journal June 1977
Projector augmented-wave method journal December 1994
Electrolyte additives for lithium ion battery electrodes: progress and perspectives journal January 2016
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set journal July 1996
Electrolyte-Induced Surface Transformation and Transition-Metal Dissolution of Fully Delithiated LiNi 0.8 Co 0.15 Al 0.05 O 2 journal June 2017
Transition Metal Dissolution, Ion Migration, Electrocatalytic Reduction and Capacity Loss in Lithium-Ion Full Cells journal December 2016
Effect of lithium difluoro(oxalate)borate (LiDFOB) additive on the performance of high-voltage lithium-ion batteries journal March 2012
Mechanisms of manganese spinels dissolution and capacity fade at high temperature journal July 2001
Suppression of Toxic Compounds Produced in the Decomposition of Lithium-Ion Battery Electrolytes journal January 2004
Study of Mn Dissolution from LiMn[sub 2]O[sub 4] Spinel Electrodes Using Rotating Ring-Disk Collection Experiments journal January 2003
Mechanistic Insight in the Function of Phosphite Additives for Protection of LiNi 0.5 Co 0.2 Mn 0.3 O 2 Cathode in High Voltage Li-Ion Cells journal April 2016
Properties and Applications of Metal Acetylacetonates journal August 1960
Comparison of Metal Ion Dissolutions from Lithium Ion Battery Cathodes journal January 2006
Preformed Anodes for High-Voltage Lithium-Ion Battery Performance: Fluorinated Electrolytes, Crosstalk, and the Origins of Impedance Rise journal January 2018
Electrolyte Reactions with the Surface of High Voltage LiNi[sub 0.5]Mn[sub 1.5]O[sub 4] Cathodes for Lithium-Ion Batteries journal January 2010
Review—Manganese Dissolution from Spinel Cathode: Few Unanswered Questions journal December 2016
Lithium-Ion Batteries: Thermal Reactions of Electrolyte with the Surface of Metal Oxide Cathode Particles journal January 2006
Electrolyte Effects on Spinel Dissolution and Cathodic Capacity Losses in 4 V Li∕Li[sub x]Mn[sub 2]O[sub 4] Rechargeable Cells journal January 1997
Qualitative and quantitative investigation of organophosphates in an electrochemically and thermally treated lithium hexafluorophosphate-based lithium ion battery electrolyte by a developed liquid chromatography-tandem quadrupole mass spectrometry method journal January 2016
Methodology for understanding interactions between electrolyte additives and cathodes: a case of the tris(2,2,2-trifluoroethyl)phosphite additive journal January 2018
Self-Discharge of LiMn[sub 2]O[sub 4]/C Li-Ion Cells in Their Discharged State journal January 1998
Chemical versus Electrochemical Electrolyte Oxidation on NMC111, NMC622, NMC811, LNMO, and Conductive Carbon journal September 2017
Ab initiomolecular dynamics for liquid metals journal January 1993
Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries journal October 2004
Surface degradation of Li1–xNi0.80Co0.15Al0.05O2 cathodes: Correlating charge transfer impedance with surface phase transformations journal June 2016
The Formation Mechanism of Fluorescent Metal Complexes at the Li x Ni 0.5 Mn 1.5 O 4−δ /Carbonate Ester Electrolyte Interface journal March 2015
Preparation of a new crystal form of manganese dioxide: λ-MnO2 journal September 1981
Understanding Transition-Metal Dissolution Behavior in LiNi 0.5 Mn 1.5 O 4 High-Voltage Spinel for Lithium Ion Batteries journal July 2013
The mechanism of HF formation in LiPF6 based organic carbonate electrolytes journal January 2012
Correlation between dissolution behavior and electrochemical cycling performance for LiNi1/3Co1/3Mn1/3O2-based cells journal June 2012
XANES Spectra of Co(ala) 3 and Co(acac) 3 in Solid and Solution journal May 1991
A bifunctional electrolyte additive for H 2 O/HF scavenging and enhanced graphite/LiNi 0.5 Co 0.2 Mn 0.3 O 2 cell performance at a high voltage journal January 2018
Cycling Behavior of NCM523/Graphite Lithium-Ion Cells in the 3–4.4 V Range: Diagnostic Studies of Full Cells and Harvested Electrodes journal September 2016
A novel electrolyte with the ability to form a solid electrolyte interface on the anode and cathode of a LiMn2O4/graphite battery journal January 2013

Similar Records

Related Subjects

25 ENERGY STORAGE
lithium-ion battery
transition metal dissolution