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Oxygen Loss in Layered Oxide Cathodes for Li-Ion Batteries: Mechanisms, Effects, and Mitigation

Journal Article · · Chemical Reviews
 [1];  [2];  [3];  [2];  [2]
  1. State Univ. of New York (SUNY), Binghamton, NY (United States); SUNY Binghamton
  2. State Univ. of New York (SUNY), Binghamton, NY (United States)
  3. State Univ. of New York (SUNY), Binghamton, NY (United States); Univ. of Warwick, Coventry (United Kingdom)
+ Show Author Affiliations

Layered lithium transition metal oxides derived from LiMO2 (M = Co, Ni, Mn, etc.) have been widely adopted as the cathodes of Li-ion batteries for portable electronics, electric vehicles, and energy storage. Oxygen loss in the layered oxides is one of the major factors leading to cycling-induced structural degradation and its associated fade in electrochemical performance. Herein, we review recent progress in understanding the phenomena of oxygen loss and the resulting structural degradation in layered oxide cathodes. We first present the major driving forces leading to the oxygen loss and then describe the associated structural degradation resulting from the oxygen loss. Here, we follow this analysis with a discussion of the kinetic pathways that enable oxygen loss, and then we address the resulting electrochemical fade. Finally, we review the possible approaches toward mitigating oxygen loss and the associated electrochemical fade as well as detail novel analytical methods for probing the oxygen loss.

Research Organization:
State Univ. of New York (SUNY), Binghamton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0012583
OSTI ID:
1864774
Journal Information:
Chemical Reviews, Journal Name: Chemical Reviews Journal Issue: 6 Vol. 122; ISSN 0009-2665
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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A First-Principles Approach to Studying the Thermal Stability of Oxide Cathode Materials journal February 2007
Factors Influencing the Irreversible Oxygen Loss and Reversible Capacity in Layered Li[Li 1/3 Mn 2/ 3 ]O 2 −Li[M]O 2 (M = Mn 0.5- y Ni 0.5- y Co 2 y and Ni 1- y Co y ) Solid Solutions journal June 2007
Atomic Structure of a Lithium-Rich Layered Oxide Material for Lithium-Ion Batteries: Evidence of a Solid Solution journal August 2011
Critical Role of Oxygen Evolved from Layered Li–Excess Metal Oxides in Lithium Rechargeable Batteries journal July 2012
Correlation Between Oxygen Vacancy, Microstrain, and Cation Distribution in Lithium-Excess Layered Oxides During the First Electrochemical Cycle journal April 2013
Neutron Diffraction and Magnetic Susceptibility Studies on a High-Voltage Li 1.2 Mn 0.55 Ni 0.15 Co 0.10 O 2 Lithium Ion Battery Cathode: Insight into the Crystal Structure journal September 2013
Investigation of Changes in the Surface Structure of Li x Ni 0.8 Co 0.15 Al 0.05 O 2 Cathode Materials Induced by the Initial Charge journal December 2013
High-Energy Layered Oxide Cathodes with Thin Shells for Improved Surface Stability journal October 2014
Insight into the Atomic Structure of High-Voltage Spinel LiNi 0.5 Mn 1.5 O 4 Cathode Material in the First Cycle journal December 2014
Thermal Instability of Cycled Li x Ni 0.5 Mn 0.5 O 2 Electrodes: An in Situ Synchrotron X-ray Powder Diffraction Study journal August 2008
Understanding the Improvement in the Electrochemical Properties of Surface Modified 5 V LiMn 1.42 Ni 0.42 Co 0.16 O 4 Spinel Cathodes in Lithium-ion Cells journal April 2009
Electrochemical and Structural Study of the Layered, “Li-Excess” Lithium-Ion Battery Electrode Material Li[Li 1/9 Ni 1/3 Mn 5/9 ]O 2 journal July 2009
Challenges for Rechargeable Li Batteries journal February 2010
Low Temperature Synthesis of Insertion Oxides for Lithium Batteries journal October 1998
Lithium Batteries and Cathode Materials journal October 2004
Ultimate Limits to Intercalation Reactions for Lithium Batteries journal October 2014
Synthesis and Characterization of Li[(Ni 0.8 Co 0.1 Mn 0.1 ) 0.8 (Ni 0.5 Mn 0.5 ) 0.2 ]O 2 with the Microscale Core−Shell Structure as the Positive Electrode Material for Lithium Batteries journal September 2005
Demonstrating Oxygen Loss and Associated Structural Reorganization in the Lithium Battery Cathode Li[Ni0.2Li0.2Mn0.6]O2 journal June 2006
Detailed Studies of a High-Capacity Electrode Material for Rechargeable Batteries, Li 2 MnO 3 −LiCo 1/3 Ni 1/3 Mn 1/3 O 2 journal March 2011
Direct Observation of Lithium Staging in Partially Delithiated LiFePO 4 at Atomic Resolution journal April 2011
Direct In situ Observation of Li 2 O Evolution on Li-Rich High-Capacity Cathode Material, Li[Ni x Li (1–2 x )/3 Mn (2– x )/3 ]O 2 (0 ≤ x ≤0.5) journal January 2014
Characterizing Oxygen Local Environments in Paramagnetic Battery Materials via 17 O NMR and DFT Calculations journal July 2016
Tuning of Thermal Stability in Layered Li(Ni x Mn y Co z )O 2 journal September 2016
Understanding Fluoroethylene Carbonate and Vinylene Carbonate Based Electrolytes for Si Anodes in Lithium Ion Batteries with NMR Spectroscopy journal July 2018
Temperature-Sensitive Structure Evolution of Lithium–Manganese-Rich Layered Oxides for Lithium-Ion Batteries journal October 2018
Collapse of LiNi 1– x – y Co x Mn y O 2 Lattice at Deep Charge Irrespective of Nickel Content in Lithium-Ion Batteries journal March 2019
Atomic and Electronic Structures of Li 0.44 MnO 2 Nanowires and Li 2 MnO 3 Byproducts in the Formation Process of LiMn 2 O 4 Nanowires journal October 2010
Coralline Glassy Lithium Phosphate-Coated LiFePO 4 Cathodes with Improved Power Capability for Lithium Ion Batteries journal March 2013
Operando X-ray Absorption Study of the Redox Processes Involved upon Cycling of the Li-Rich Layered Oxide Li 1.20 Mn 0.54 Co 0.13 Ni 0.13 O 2 in Li Ion Batteries journal March 2014
Understanding the Effect of Co 3+ Substitution on the Electrochemical Properties of Lithium-Rich Layered Oxide Cathodes for Lithium-Ion Batteries journal September 2014
Electron–Water Interactions and Implications for Liquid Cell Electron Microscopy journal September 2014
Insight into the Atomic Structure of Cycled Lithium-Rich Layered Oxide Li 1.20 Mn 0.54 Co 0.13 Ni 0.13 O 2 Using HAADF STEM and Electron Nanodiffraction journal December 2014
Mesoporous Co 3 O 4 Nanowire Arrays for Lithium Ion Batteries with High Capacity and Rate Capability journal January 2008
Corrosion/Fragmentation of Layered Composite Cathode and Related Capacity/Voltage Fading during Cycling Process journal July 2013
First Evidence of Manganese–Nickel Segregation and Densification upon Cycling in Li-Rich Layered Oxides for Lithium Batteries journal July 2013
Bubble and Pattern Formation in Liquid Induced by an Electron Beam journal December 2013
Mitigating Voltage Fade in Cathode Materials by Improving the Atomic Level Uniformity of Elemental Distribution journal April 2014
Nanoscale Morphological and Chemical Changes of High Voltage Lithium–Manganese Rich NMC Composite Cathodes with Cycling journal July 2014
Evolution of Lattice Structure and Chemical Composition of the Surface Reconstruction Layer in Li 1.2 Ni 0.2 Mn 0.6 O 2 Cathode Material for Lithium Ion Batteries journal December 2014
Nano-sized transition-metal oxides as negative-electrode materials for lithium-ion batteries journal September 2000
Issues and challenges facing rechargeable lithium batteries journal November 2001
Building better batteries journal February 2008
Promise and reality of post-lithium-ion batteries with high energy densities journal March 2016
Soft X-ray microscopy at a spatial resolution better than 15 nm journal June 2005
Raising the cycling stability of aqueous lithium-ion batteries by eliminating oxygen in the electrolyte journal August 2010
Gas–solid interfacial modification of oxygen activity in layered oxide cathodes for lithium-ion batteries journal July 2016
Intragranular cracking as a critical barrier for high-voltage usage of layer-structured cathode for lithium-ion batteries journal January 2017
Understanding materials challenges for rechargeable ion batteries with in situ transmission electron microscopy journal August 2017
Distinct charge dynamics in battery electrodes revealed by in situ and operando soft X-ray spectroscopy journal October 2013
Surface reconstruction and chemical evolution of stoichiometric layered cathode materials for lithium-ion batteries journal March 2014
Complex structural dynamics of nanocatalysts revealed in Operando conditions by correlated imaging and spectroscopy probes journal June 2015
Metal segregation in hierarchically structured cathode materials for high-energy lithium batteries journal January 2016
High-energy cathode material for long-life and safe lithium batteries journal March 2009
Universal energy-level alignment of molecules on metal oxides journal November 2011
Reversible anionic redox chemistry in high-capacity layered-oxide electrodes journal July 2013
Origin of voltage decay in high-capacity layered oxide electrodes journal December 2014
Sustainability and in situ monitoring in battery development journal December 2016
Elucidating anionic oxygen activity in lithium-rich layered oxides journal March 2018
Biomacromolecules enabled dendrite-free lithium metal battery and its origin revealed by cryo-electron microscopy journal January 2020
A reflection on lithium-ion battery cathode chemistry journal March 2020
Approaching the capacity limit of lithium cobalt oxide in lithium ion batteries via lanthanum and aluminium doping journal June 2018
Nucleation of dislocations and their dynamics in layered oxide cathode materials during battery charging journal July 2018
Tailoring grain boundary structures and chemistry of Ni-rich layered cathodes for enhanced cycle stability of lithium-ion batteries journal June 2018
Evolution of redox couples in Li- and Mn-rich cathode materials and mitigation of voltage fade by reducing oxygen release journal July 2018
Improving cyclability of Li metal batteries at elevated temperatures and its origin revealed by cryo-electron microscopy journal July 2019
High-nickel layered oxide cathodes for lithium-based automotive batteries journal January 2020
The interplay between thermodynamics and kinetics in the solid-state synthesis of layered oxides journal May 2020
Bulk fatigue induced by surface reconstruction in layered Ni-rich cathodes for Li-ion batteries journal August 2020
Injection of oxygen vacancies in the bulk lattice of layered cathodes journal April 2019
Cryo-STEM mapping of solid–liquid interfaces and dendrites in lithium-metal batteries journal August 2018
Surface Chemistry Dependence on Aluminum Doping in Ni-rich LiNi0.8Co0.2−yAlyO2 Cathodes journal November 2019
High rate capability caused by surface cubic spinels in Li-rich layer-structured cathodes for Li-ion batteries journal October 2013
Chemical and Structural Stability of Lithium-Ion Battery Electrode Materials under Electron Beam journal July 2014
Intrinsic Origins of Crack Generation in Ni-rich LiNi0.8Co0.1Mn0.1O2 Layered Oxide Cathode Material journal January 2017
Enhancing the performances of Li-ion batteries by carbon-coating: present and future journal January 2012
A new O3-type layered oxide cathode with high energy/power density for rechargeable Na batteries journal January 2015
Uncovering the roles of oxygen vacancies in cation migration in lithium excess layered oxides journal January 2014
Profiling the nanoscale gradient in stoichiometric layered cathode particles for lithium-ion batteries journal January 2014
A hydrolysis-hydrothermal route for the synthesis of ultrathin LiAlO 2 -inlaid LiNi 0.5 Co 0.2 Mn 0.3 O 2 as a high-performance cathode material for lithium ion batteries journal January 2015
The intriguing question of anionic redox in high-energy density cathodes for Li-ion batteries journal January 2016
Performance and design considerations for lithium excess layered oxide positive electrode materials for lithium ion batteries journal January 2016
Mitigation of layer to spinel conversion of a lithium-rich layered oxide cathode by substitution of Al in a lithium ion battery journal January 2015
Spatially resolved surface valence gradient and structural transformation of lithium transition metal oxides in lithium-ion batteries journal January 2016
Electrolyte additives for lithium ion battery electrodes: progress and perspectives journal January 2016
Enhanced capacity and lower mean charge voltage of Li-rich cathodes for lithium ion batteries resulting from low-temperature electrochemical activation journal January 2017
Overcoming the chemical instability on exposure to air of Ni-rich layered oxide cathodes by coating with spinel LiMn 1.9 Al 0.1 O 4 journal January 2016
A review of Ni-based layered oxides for rechargeable Li-ion batteries journal January 2017
Intrinsic origin of intra-granular cracking in Ni-rich layered oxide cathode materials journal January 2018
High performance manganese-based layered oxide cathodes: overcoming the challenges of sodium ion batteries journal January 2017
Nanostructured Li 2 MnO 3 : a disordered rock salt type structure for high energy density Li ion batteries journal January 2017
Effect of cobalt content on the electrochemical properties and structural stability of NCA type cathode materials journal January 2018
Stabilizing nickel-rich layered oxide cathodes by magnesium doping for rechargeable lithium-ion batteries journal January 2019
Mitigating oxygen release in anionic-redox-active cathode materials by cationic substitution through rational design journal January 2018
Revisiting the charge compensation mechanisms in LiNi 0.8 Co 0.2−y Al y O 2 systems journal January 2019
A cyclic electrochemical strategy to produce acetylene from CO 2 , CH 4 , or alternative carbon sources journal January 2020
Origins of capacity and voltage fading of LiCoO 2 upon high voltage cycling journal January 2019
Advances in soft X-ray RIXS for studying redox reaction states in batteries journal January 2020
Suppressing H2–H3 phase transition in high Ni–low Co layered oxide cathode material by dual modification journal January 2020
The insulator-metal transition upon lithium deintercalation from LiCoO2: electronic properties and 7Li NMR study journal January 1999
Li2MnO3-stabilized LiMO2 (M = Mn, Ni, Co) electrodes for lithium-ion batteries journal January 2007
Nanostructured electrode materials for electrochemical energy storage and conversion journal January 2008
Functional surface modifications of a high capacity layered Li[Li0.2Mn0.54Ni0.13Co0.13]O2 cathode journal January 2010
Ab initio molecular dynamics simulations of the initial stages of solid–electrolyte interphase formation on lithium ion battery graphitic anodes journal January 2010
Role of surface coating on cathode materials for lithium-ion batteries journal January 2010
Structural evolution of layered Li1.2Ni0.2Mn0.6O2 upon electrochemical cycling in a Li rechargeable battery journal January 2010
Identifying surface structural changes in layered Li-excess nickel manganese oxides in high voltage lithium ion batteries: A joint experimental and theoretical study journal January 2011
Thermal stability and phase transformation of electrochemically charged/discharged LiMnPO4 cathode for Li-ion batteries journal January 2011
Voltage, stability and diffusion barrier differences between sodium-ion and lithium-ion intercalation materials journal January 2011
Mechanism of capacity fade of MCMB/Li1.1[Ni1/3Mn1/3Co1/3]0.9O2 cell at elevated temperature and additives to improve its cycle life journal January 2011
The stability of the SEI layer, surface composition and the oxidation state of transition metals at the electrolyte–cathode interface impacted by the electrochemical cycling: X-ray photoelectron spectroscopy investigation journal January 2012
Structural evolution and the capacity fade mechanism upon long-term cycling in Li-rich cathode material journal January 2012
Layered lithium transition metal oxide cathodes towards high energy lithium-ion batteries journal January 2012
Understanding structural defects in lithium-rich layered oxide cathodes journal January 2012
Surface nitridation of Li-rich layered Li(Li0.17Ni0.25Mn0.58)O2 oxide as cathode material for lithium-ion battery journal January 2012
Probing the electrode/electrolyte interface in the lithium excess layered oxide Li1.2Ni0.2Mn0.6O2 journal January 2013
Correlating cation ordering and voltage fade in a lithium–manganese-rich lithium-ion battery cathode oxide: a joint magnetic susceptibility and TEM study journal January 2013
A perspective on the high-voltage LiMn1.5Ni0.5O4 spinel cathode for lithium-ion batteries journal January 2014
Investigating phase transformation in the Li1.2Co0.1Mn0.55Ni0.15O2 lithium-ion battery cathode during high-voltage hold (4.5 V) via magnetic, X-ray diffraction and electron microscopy studies journal January 2013
Surface degradation of Li1–xNi0.80Co0.15Al0.05O2 cathodes: Correlating charge transfer impedance with surface phase transformations journal June 2016
Diamond Light Source: status and perspectives
  • Materlik, Gerhard; Rayment, Trevor; Stuart, David I.
  • Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 373, Issue 2036 https://doi.org/10.1098/rsta.2013.0161
journal March 2015
Defect Physics, Delithiation Mechanism, and Electronic and Ionic Conduction in Layered Lithium Manganese Oxide Cathode Materials journal February 2015
Vacancy Ordering in O 3 -Type Layered Metal Oxide Sodium-Ion Battery Cathodes journal December 2015
VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data journal October 2011
Best practices for operando depth-resolving battery experiments journal February 2020
Electrodes with High Power and High Capacity for Rechargeable Lithium Batteries journal February 2006
High-Resolution Scanning X-ray Diffraction Microscopy journal July 2008
Unlocking the Potential of Cation-Disordered Oxides for Rechargeable Lithium Batteries journal January 2014
Chemical contrast in X-ray microscopy and spatially resolved XANES spectroscopy of organic specimens journal November 1992
Visualization of O-O peroxo-like dimers in high-capacity layered oxides for Li-ion batteries journal December 2015
Atomic structure of sensitive battery materials and interfaces revealed by cryo–electron microscopy journal October 2017
Layered-to-Spinel Phase Transition in Li[sub x]MnO[sub 2] journal January 2001
TEM Study of Electrochemical Cycling-Induced Damage and Disorder in LiCoO[sub 2] Cathodes for Rechargeable Lithium Batteries journal January 1999
Oxidative Electrolyte Solvent Degradation in Lithium-Ion Batteries: An In Situ Differential Electrochemical Mass Spectrometry Investigation journal January 1999
Understanding the Anomalous Capacity of Li / Li [ NixLi ( 1 / 3 − 2x / 3 ) Mn ( 2 / 3 − x / 3 ) ]  O2 Cells Using In Situ X-Ray Diffraction and Electrochemical Studies journal January 2002
Comparison of the Electrochemical Behaviors of Stoichiometric LiNi[sub 1/3]Co[sub 1/3]Mn[sub 1/3]O[sub 2] and Lithium Excess Li[sub 1.03](Ni[sub 1/3]Co[sub 1/3]Mn[sub 1/3])[sub 0.97]O[sub 2] journal January 2004
Characterization of Thin-Film Rechargeable Lithium Batteries with Lithium Cobalt Oxide Cathodes journal January 1996
A Comparative Study of Synthetic Graphite and Li Electrodes in Electrolyte Solutions Based on Ethylene Carbonate-Dimethyl Carbonate Mixtures journal January 1996
Characterization of Layered Lithium Nickel Manganese Oxides Synthesized by a Novel Oxidative Coprecipitation Method and Their Electrochemical Performance as Lithium Insertion Electrode Materials journal January 1998
Capacity Fade Mechanisms and Side Reactions in Lithium-Ion Batteries journal January 1998
The Spinel Phase of LiMn[sub 2]O[sub 4] as a Cathode in Secondary Lithium Cells journal January 1991
Suppression of Mn Dissolution in Spinel Cathodes by Trapping the Protons within Layered Oxide Cathodes journal January 2007
Cycle-Life Characterization of Automotive Lithium-Ion Batteries with LiNiO[sub 2] Cathode journal January 2009
Kinetics Study of the High Potential Range of Lithium-Rich Transition-Metal Oxides for Lithium-Ion Batteries by Electrochemical Methods journal January 2010
Synthesis–Structure–Property Relations in Layered, “Li-excess” Oxides Electrode Materials Li[Li[sub 1/3−2x/3]Ni[sub x]Mn[sub 2/3−x/3]]O[sub 2] (x=1/3, 1/4, and 1/5) journal January 2010
Influence of NCM Particle Cracking on Kinetics of Lithium-Ion Batteries with Liquid or Solid Electrolyte journal June 2020
State-of-Charge Dependence of Mechanical Response of Lithium-Ion Batteries: A Result of Internal Stress journal January 2018
LiCoO 2 Degradation Behavior in the High-Voltage Phase Transition Region and Improved Reversibility with Surface Coating journal November 2016
Voltage Fade of Layered Oxides: Its Measurement and Impact on Energy Density journal January 2013
The Effect of Battery Separator Properties on Thermal Ramp, Overcharge and Short Circuiting of Rechargeable Li-Ion Batteries journal January 2019
Effect of Residual Lithium Compounds on Layer Ni-Rich Li[Ni 0.7 Mn 0.3 ]O 2 journal January 2014
Single-Crystalline Particles: An Effective Way to Ameliorate the Intragranular Cracking, Thermal Stability, and Capacity Fading of the LiNi 0.6 Co 0.2 Mn 0.2 O 2 Electrodes journal January 2018
Long-Term Low-Rate Cycling of LiCoO 2 /Graphite Li-Ion Cells at 55°C journal January 2012
Analysis of Rate-Limiting Factors in Thick Electrodes for Electric Vehicle Applications journal January 2018
Changing of SEI Film and Electrochemical Properties about MCMB Electrodes during Long-Term Charge/Discharge Cycles journal January 2013
Correlative Microscopy-Based Approach for Analyzing Microscopic Impurities in Carbon Black for Lithium-Ion Battery Applications journal January 2019
Decomposition of LiPF 6 in High Energy Lithium-Ion Batteries Studied with Online Electrochemical Mass Spectrometry journal January 2016
A Wide Range of Testing Results on an Excellent Lithium-Ion Cell Chemistry to be used as Benchmarks for New Battery Technologies journal January 2019
The Role of Oxygen Release from Li- and Mn-Rich Layered Oxides during the First Cycles Investigated by On-Line Electrochemical Mass Spectrometry journal December 2016
Enhanced Electrochemical Performance of Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 via L-Ascorbic Acid-Based Treatment as Cathode Material for Li-Ion Batteries journal January 2018
Understanding the structure and structural degradation mechanisms in high-voltage, lithium-manganese–rich lithium-ion battery cathode oxides: A review of materials diagnostics journal January 2015
X-Ray Determination of Electron-Density Distributions in Oxides, MgO, MnO, CoO, and NiO, and Atomic Scattering Factors of their Constituent Atoms
  • Sasaki, Satoshi; Fujino, Kiyoshi; TakÉUchi, Yoshio
  • Proceedings of the Japan Academy. Ser. B: Physical and Biological Sciences, Vol. 55, Issue 2 https://doi.org/10.2183/pjab.55.43
journal January 1979
The Formation, Detriment and Solution of Residual Lithium Compounds on Ni-Rich Layered Oxides in Lithium-Ion Batteries journal December 2020
Application of Operando X-ray Diffractometry in Various Aspects of the Investigations of Lithium/Sodium-Ion Batteries journal November 2018
A Bottom-Up Approach to Lithium-Ion Battery Cost Modeling with a Focus on Cathode Active Materials journal February 2019
Comparative Issues of Cathode Materials for Li-Ion Batteries journal March 2014
Optimization of Layered Cathode Materials for Lithium-Ion Batteries journal July 2016
Lithium Ion Battery Fire And Explosion journal January 2005

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Related Subjects

36 MATERIALS SCIENCE
lithium ion batteries
oxygen loss
structure stability