skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Coupling between oxygen redox and cation migration explains unusual electrochemistry in lithium-rich layered oxides

Journal Article · · Nature Communications

Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
USDOE
DOE Contract Number:
AC02-76SF00515
OSTI ID:
1418167
Journal Information:
Nature Communications, Vol. 8, Issue 1; ISSN 2041-1723
Country of Publication:
United States
Language:
English

References (97)

Reversible anionic redox chemistry in high-capacity layered-oxide electrodes journal July 2013
Crystal and electronic structure analysis and thermodynamic stabilities for electrochemically or chemically delithiated Li1.2−xMn0.54Ni0.13Co0.13O2 journal July 2016
Projector augmented-wave method journal December 1994
Understanding the Roles of Anionic Redox and Oxygen Release during Electrochemical Cycling of Lithium-Rich Layered Li 4 FeSbO 6 journal April 2015
Voltage- and time-dependent valence state transition in cobalt oxide catalysts during the oxygen evolution reaction journal April 2020
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
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
Structural transformation of a lithium-rich Li1.2Co0.1Mn0.55Ni0.15O2 cathode during high voltage cycling resolved by in situ X-ray diffraction journal May 2013
Modular soft x-ray spectrometer for applications in energy sciences and quantum materials journal January 2017
Unravelling structural ambiguities in lithium- and manganese-rich transition metal oxides journal October 2015
Ultimate Limits to Intercalation Reactions for Lithium Batteries journal October 2014
Different oxygen redox participation for bulk and surface: A possible global explanation for the cycling mechanism of Li1.20Mn0.54Co0.13Ni0.13O2 journal August 2013
Correlating hysteresis and voltage fade in lithium- and manganese-rich layered transition-metal oxide electrodes journal August 2013
The irreversible momentum of clean energy journal January 2017
Uncovering the roles of oxygen vacancies in cation migration in lithium excess layered oxides journal January 2014
Simulation of First-Charge Oxygen-Dimerization and Mn-Migration in Li-Rich Layered Oxides x Li 2 MnO 3 ·(1 – x )Li M O 2 and Implications for Voltage Fade journal March 2017
Soft-x-ray-absorption studies of the location of extra charges induced by substitution in controlled-valence materials journal September 1991
Lithium Extraction Mechanism in Li-Rich Li 2 MnO 3 Involving Oxygen Hole Formation and Dimerization journal September 2016
Understanding the Role of Ni in Stabilizing the Lithium-Rich High-Capacity Cathode Material Li[Ni x Li (1–2 x )/3 Mn (2– x )/3 ]O 2 (0 ≤ x ≤ 0.5) journal December 2014
In Situ X-ray Diffraction Study of Layered Li–Ni–Mn–Co Oxides: Effect of Particle Size and Structural Stability of Core–Shell Materials journal December 2015
Exploring Oxygen Activity in the High Energy P2-Type Na 0.78 Ni 0.23 Mn 0.69 O 2 Cathode Material for Na-Ion Batteries journal March 2017
Reducing Dzyaloshinskii-Moriya interaction and field-free spin-orbit torque switching in synthetic antiferromagnets journal May 2021
Resolving the degradation pathways in high-voltage oxides for high-energy-density lithium-ion batteries; Alternation in chemistry, composition and crystal structures journal June 2017
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
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
Finite temperature effects on the X-ray absorption spectra of lithium compounds: First-principles interpretation of X-ray Raman measurements journal January 2014
Origin of stabilization and destabilization in solid-state redox reaction of oxide ions for lithium-ion batteries journal December 2016
Direct observation of reversible oxygen anion redox reaction in Li-rich manganese oxide, Li 2 MnO 3 , studied by soft X-ray absorption spectroscopy journal January 2016
First-charge instabilities of layered-layered lithium-ion-battery materials journal January 2015
Soft X-Ray Irradiation Effects of Li2O2, Li2CO3 and Li2O Revealed by Absorption Spectroscopy journal November 2012
Interferometer-controlled scanning transmission X-ray microscopes at the Advanced Light Source journal February 2003
Role of Electronic Structure in the Susceptibility of Metastable Transition-Metal Oxide Structures to Transformation journal December 2004
Contrasting behavior of homovalent-substituted and hole-doped systems: O K -edge spectra from LaNi 1 x M x O 3 ( M =Mn, Fe, and Co) and La 1 x Sr x MnO 3 journal May 1994
Soft X-ray microscopy and spectroscopy at the molecular environmental science beamline at the Advanced Light Source journal February 2006
Anionic redox processes for electrochemical devices journal January 2016
The intriguing question of anionic redox in high-energy density cathodes for Li-ion batteries journal January 2016
Microstructural investigation of LixNi1/3Mn1/3Co1/3O2 (x ≤ 1) and its aged products via magnetic and diffraction study journal December 2012
High-resolution X-ray luminescence extension imaging journal February 2021
Structural and Chemical Evolution of the Layered Li-Excess Li x MnO 3 as a Function of Li Content from First-Principles Calculations journal June 2014
The structural and chemical origin of the oxygen redox activity in layered and cation-disordered Li-excess cathode materials journal May 2016
High-efficiency in situ resonant inelastic x-ray scattering (iRIXS) endstation at the Advanced Light Source journal March 2017
Visualization of O-O peroxo-like dimers in high-capacity layered oxides for Li-ion batteries journal December 2015
Oxygen 1 s x-ray-absorption edges of transition-metal oxides journal September 1989
Reversible Oxygen Participation to the Redox Processes Revealed for Li 1.20 Mn 0.54 Co 0.13 Ni 0.13 O 2 journal January 2013
Soft X-ray Absorption Spectroscopic and Raman Studies on Li 1.2 Ni 0.2 Mn 0.6 O 2 for Lithium-Ion Batteries journal November 2012
Investigation of the Charge Compensation Mechanism on the Electrochemically Li-Ion Deintercalated Li 1 - x Co 1/3 Ni 1/3 Mn 1/3 O 2 Electrode System by Combination of Soft and Hard X-ray Absorption Spectroscopy journal December 2005
Charge-compensation in 3d-transition-metal-oxide intercalation cathodes through the generation of localized electron holes on oxygen journal March 2016
Examining Hysteresis in Composite x Li 2 MnO 3 ·(1– x )LiMO 2 Cathode Structures journal March 2013
Investigation of the Charge Compensation Mechanism on the Electrochemically Li-Ion Deintercalated Li1-xCo1/3Ni1/3Mn1/3O2 Electrode System by Combination of Soft and Hard X-Ray Absorption Spectroscopy. journal March 2006
Direct Experimental Probe of the Ni(II)/Ni(III)/Ni(IV) Redox Evolution in LiNi 0.5 Mn 1.5 O 4 Electrodes journal November 2015
Quantifying Hysteresis and Voltage Fade in xLi 2 MnO 3 (1-x)LiMn 0.5 Ni 0.5 O 2 Electrodes as a Function of Li 2 MnO 3 Content journal December 2013
Improved treatment of exact exchange in Quantum ESPRESSO journal May 2017
Direct observation of reversible charge compensation by oxygen ion in Li-rich manganese layered oxide positive electrode material, Li1.16Ni0.15Co0.19Mn0.50O2 journal February 2015
Building better batteries journal February 2008
Charge compensation mechanisms in Li1.16Ni0.15Co0.19Mn0.50O2 positive electrode material for Li-ion batteries analyzed by a combination of hard and soft X-ray absorption near edge structure journal January 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
Vacancy-induced MnO 6 distortion and its impacts on structural transition of Li 2 MnO 3 journal January 2017
Structure of Lithium Peroxide journal September 2011
Spectroscopic fingerprints of valence and spin states in manganese oxides and fluorides text January 2012
Review—Lithium-Excess Layered Cathodes for Lithium Rechargeable Batteries journal January 2015
Generalized Gradient Approximation Made Simple journal October 1996
QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials journal September 2009
Resonant inelastic x-ray scattering as a probe of optical scale excitations in strongly electron-correlated systems: quasi-localized view preprint January 1999
From ultrasoft pseudopotentials to the projector augmented-wave method journal January 1999
Dichotomy in the Lithiation Pathway of Ellipsoidal and Platelet LiFePO 4 Particles Revealed through Nanoscale Operando State-of-Charge Imaging journal May 2015
Controlled-valence properties of La 1 x Sr x FeO 3 and La 1 x Sr x MnO 3 studied by soft-x-ray absorption spectroscopy journal August 1992
Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study journal January 1998
Anion Redox Chemistry in the Cobalt Free 3d Transition Metal Oxide Intercalation Electrode Li[Li 0.2 Ni 0.2 Mn 0.6 ]O 2 journal August 2016
Why LiFePO 4 is a safe battery electrode: Coulomb repulsion induced electron-state reshuffling upon lithiation journal January 2015
Strong Oxygen Participation in the Redox Governing the Structural and Electrochemical Properties of Na-Rich Layered Oxide Na 2 IrO 3 journal October 2016
Correlation Between Oxygen Vacancy, Microstrain, and Cation Distribution in Lithium-Excess Layered Oxides During the First Electrochemical Cycle journal April 2013
Origin of voltage decay in high-capacity layered oxide electrodes journal December 2014
Distinct charge dynamics in battery electrodes revealed by in situ and operando soft X-ray spectroscopy journal October 2013
Resonant inelastic X-ray scattering as a probe of optical scale excitations in strongly electron-correlated systems: quasi-localized view journal October 2000
Potential hysteresis between charge and discharge reactions in Li1.2Ni0.13Mn0.54Co0.13O2 for lithium ion batteries journal February 2017
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set journal July 1996
Electronic structure of AlFeN films exhibiting crystallographic orientation change from c- to a-axis with Fe concentrations and annealing effect journal February 2020
Evidence for holes on oxygen sites in the high- T c superconductors La 2 x Sr x CuO 4 and YBa 2 Cu 3 O 7 y journal April 1988
Intermediate honeycomb ordering to trigger oxygen redox chemistry in layered battery electrode journal April 2016
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
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
Quantitative probe of the transition metal redox in battery electrodes through soft x-ray absorption spectroscopy journal September 2016
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT journal June 2005
Scanning transmission X-ray microscopy at a bending magnet beamline at the Advanced Light Source journal March 2003
The origins and mechanism of phase transformation in bulk Li 2 MnO 3 : first-principles calculations and experimental studies journal January 2015
Spectroscopic fingerprints of valence and spin states in manganese oxides and fluorides journal May 2013
Gas–solid interfacial modification of oxygen activity in layered oxide cathodes for lithium-ion batteries journal July 2016
Requirements for reversible extra-capacity in Li-rich layered oxides for Li-ion batteries journal January 2017
Resonant inelastic x-ray scattering studies of elementary excitations journal June 2011
Relations between the Concentrations of Imperfections in Crystalline Solids book January 1956
Structure of Li2MnO3 with different degrees of defects journal January 2010
Editors' Choice—Practical Assessment of Anionic Redox in Li-Rich Layered Oxide Cathodes: A Mixed Blessing for High Energy Li-Ion Batteries journal January 2016
Character of Holes in Li x Ni 1 x O and Their Magnetic Behavior journal January 1989
First Evidence of Manganese–Nickel Segregation and Densification upon Cycling in Li-Rich Layered Oxides for Lithium Batteries journal July 2013
Redox activity of surface oxygen anions in oxygen-deficient perovskite oxides during electrochemical reactions journal January 2015
Quantitative Analysis of Transition-Metal Migration Induced Electrochemically in Lithium-Rich Layered Oxide Cathode and Its Contribution to Properties at High and Low Temperatures journal November 2016
Role of Electronic Structure in the Susceptibility of Metastable Transition-Metal Oxide Structures to Transformation journal October 2004

Cited By (41)

A Cobalt‐Free Li(Li 0.16 Ni 0.19 Fe 0.18 Mn 0.46 )O 2 Cathode for Lithium‐Ion Batteries with Anionic Redox Reactions journal February 2019
High-Performance Li-Rich Layered Transition Metal Oxide Cathode Materials for Li-Ion Batteries journal January 2019
Understanding Performance Degradation in Cation‐Disordered Rock‐Salt Oxide Cathodes journal July 2019
Material Design Concept of Lithium‐Excess Electrode Materials with Rocksalt‐Related Structures for Rechargeable Non‐Aqueous Batteries journal October 2018
In Situ Probing Multiple-Scale Structures of Energy Materials for Li-Ion Batteries journal May 2019
Oxygen release and oxygen redox journal July 2018
Voltage decay and redox asymmetry mitigation by reversible cation migration in lithium-rich layered oxide electrodes journal January 2020
Fundamental understanding and practical challenges of anionic redox activity in Li-ion batteries journal April 2018
Li-Rich Layered Oxides and Their Practical Challenges: Recent Progress and Perspectives journal March 2019
Unraveling the Voltage Decay Phenomenon in Li‐Rich Layered Oxide Cathode of No Oxygen Activity journal October 2019
Enhanced cycling stability of boron-doped lithium-rich layered oxide cathode materials by suppressing transition metal migration journal January 2019
Oxygen Release and Surface Degradation of Li- and Mn-Rich Layered Oxides in Variation of the Li 2 MnO 3 Content journal January 2018
Anionic Redox Activity in a Newly Zn-Doped Sodium Layered Oxide P2-Na 2/3 Mn 1− y Zn y O 2 (0 < y < 0.23) journal October 2018
Eliminating Transition Metal Migration and Anionic Redox to Understand Voltage Hysteresis of Lithium‐Rich Layered Oxides journal January 2020
Role of transition metals in a charge transfer mechanism and oxygen removal in Li 1.17 Ni 0.17 Mn 0.5 Co 0.17 O 2 : experimental and first-principles analysis journal January 2018
Ultrahigh power and energy density in partially ordered lithium-ion cathode materials journal March 2020
Metal–oxygen decoordination stabilizes anion redox in Li-rich oxides journal February 2019
Suppression of Voltage Decay through Manganese Deactivation and Nickel Redox Buffering in High-Energy Layered Lithium-Rich Electrodes journal May 2018
Injection of oxygen vacancies in the bulk lattice of layered cathodes journal April 2019
Dissociate lattice oxygen redox reactions from capacity and voltage drops of battery electrodes journal February 2020
Simultaneously tuning cationic and anionic redox in a P2-Na 0.67 Mn 0.75 Ni 0.25 O 2 cathode material through synergic Cu/Mg co-doping journal January 2019
Co-regulating the surface and bulk structure of Li-rich layered oxides by a phosphor doping strategy for high-energy Li-ion batteries journal January 2019
Voltage fade mitigation in the cationic dominant lithium-rich NCM cathode journal October 2019
Li–Ti Cation Mixing Enhanced Structural and Performance Stability of Li‐Rich Layered Oxide journal July 2019
Surface Doping to Enhance Structural Integrity and Performance of Li-Rich Layered Oxide journal October 2018
Horizons for Li-Ion Batteries Relevant to Electro-Mobility: High-Specific-Energy Cathodes and Chemically Active Separators journal July 2018
Retarding Phase Transformation During Cycling in a Lithium‐ and Manganese‐Rich Cathode Material by Optimizing Synthesis Conditions journal January 2019
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
A Cobalt‐Free Li(Li 0.17 Ni 0.17 Fe 0.17 Mn 0.49 )O 2 Cathode with More Oxygen‐Involving Charge Compensation for Lithium‐Ion Batteries journal April 2019
Fingerprint Oxygen Redox Reactions in Batteries through High-Efficiency Mapping of Resonant Inelastic X-ray Scattering journal January 2019
High-discharge-voltage lithium-rich layered-oxide cathode materials based on low oxygen vacancy journal January 2019
Unveiling the origin of high reversible capacity in Li-rich layered oxide in Li-ion batteries journal September 2019
Editors' Choice—State of Charge Dependent Resistance Build-Up in Li- and Mn-Rich Layered Oxides during Lithium Extraction and Insertion journal January 2019
A First-Principles and Experimental Investigation of Nickel Solubility into the P2 Na x CoO 2 Sodium-Ion Cathode journal August 2018
First-Cycle Simulation for Li-Rich Layered Oxide Cathode Material x Li 2 MnO 3 (1- x )Li M O 2 ( x = 0.4) journal January 2018
Surface Degradation and Chemical Electrolyte Oxidation Induced by the Oxygen Released from Layered Oxide Cathodes in Li−Ion Batteries journal March 2019
Manganese oxidation as the origin of the anomalous capacity of Mn-containing Li-excess cathode materials journal July 2019
Li‐doping stabilized P2‐Li 0.2 Na 1.0 Mn 0.8 O 2 sodium ion cathode with oxygen redox activity journal December 2019
Chemical and structural origin of lattice oxygen oxidation in Co–Zn oxyhydroxide oxygen evolution electrocatalysts journal March 2019
Surface Modification of Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 Cathode Material with Al 2 O 3 /SiO 2 Composite for Lithium-Ion Batteries journal January 2019
A Comprehensive Analysis of the Interphasial and Structural Evolution over Long‐Term Cycling of Ultrahigh‐Nickel Cathodes in Lithium‐Ion Batteries journal October 2019

Related Subjects