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

Title: Surface-to-bulk redox coupling through thermally-driven Li redistribution in Li- and Mn-rich layered cathode materials

Journal Article · · Journal of the American Chemical Society
 [1];  [2];  [3]; ORCiD logo [4];  [2];  [5];  [5]; ORCiD logo [5];  [5]; ORCiD logo [6];  [6];  [7];  [2];  [2]; ORCiD logo [8]; ORCiD logo [8]; ORCiD logo [9]; ORCiD logo [10]; ORCiD logo [10];  [2] more »;  [2] « less
  1. SLAC National Accelerator Lab., Menlo Park, CA (United States); Dalian Univ. of Technology, Dalian (China)
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States); Univ. of Chinese Academy of Sciences, Beijing (China)
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  5. National Inst. of Standards and Technology (NIST), Boulder, CO (United States)
  6. Stanford Univ., Stanford, CA (United States)
  7. SLAC National Accelerator Lab., Menlo Park, CA (United States); Pohang Accelerator Lab, Pohang (Republic of Korea)
  8. Dalian Univ. of Technology, Dalian (China)
  9. Univ. of Chinese Academy of Sciences, Beijing (China)
  10. Brookhaven National Lab. (BNL), Upton, NY (United States)
+ Show Author Affiliations

Li- and Mn-rich (LMR) layered cathode materials have demonstrated impressive capacity and specific energy density thanks to their intertwined redox centers including transition metal cations and oxygen anions. Although tremendous efforts have been devoted to the investigation of the electrochemically-driven redox evolution in LMR cathode at ambient temperature, their behavior under a mildly elevated temperature (up to ~100 °C), with or without electrochemical driving force, remains largely unexplored. Here we show a systematic study of the thermally-driven surface-to-bulk redox coupling effect in charged Li1.2Ni0.15Co0.1Mn0.55O2. We for the first time observed a charge transfer between the bulk oxygen anions and the surface transition metal cations under ~100 °C, which is attributed to the thermally-driven redistribution of Li ions. As a result, this finding highlights the non-equilibrium state and dynamic nature of the LMR material at deeply delithiated state upon a mild temperature perturbation.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II); SLAC National Accelerator Laboratory, Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL); Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES); Chinese Scholarship Council (CSC)
Grant/Contract Number:
SC0012704; AC02-76SF00515; SC0012704; AC02-06CH11357
OSTI ID:
1542786
Alternate ID(s):
OSTI ID: 1659755; OSTI ID: 1688801; OSTI ID: 1594929
Report Number(s):
BNL--211864-2019-JAAM
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 30 Vol. 141; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

References (47)

Electrochemical kinetics of the 0.5Li2MnO3·0.5LiMn0.42Ni0.42Co0.16O2 ‘composite’ layered cathode material for lithium-ion batteries journal January 2012
Evolution of redox couples in Li- and Mn-rich cathode materials and mitigation of voltage fade by reducing oxygen release journal July 2018
In Situ Three-Dimensional Synchrotron X-Ray Nanotomography of the (De)lithiation Processes in Tin Anodes journal March 2014
L-edge spectroscopy of dilute, radiation-sensitive systems using a transition-edge-sensor array journal December 2017
Review of the U.S. Department of Energy’s “Deep Dive” Effort to Understand Voltage Fade in Li- and Mn-Rich Cathodes journal October 2015
Characterising thermal runaway within lithium-ion cells by inducing and monitoring internal short circuits journal January 2017
Mesoscale Battery Science: The Behavior of Electrode Particles Caught on a Multispectral X-ray Camera journal June 2018
The structural and chemical origin of the oxygen redox activity in layered and cation-disordered Li-excess cathode materials journal May 2016
Reversible anionic redox chemistry in high-capacity layered-oxide electrodes journal July 2013
Coupling of electrochemically triggered thermal and mechanical effects to aggravate failure in a layered cathode journal June 2018
High Reversibility of Lattice Oxygen Redox Quantified by Direct Bulk Probes of Both Anionic and Cationic Redox Reactions journal February 2019
High-capacity electrode materials for electrochemical energy storage: Role of nanoscale effects journal June 2015
Anionic and cationic redox and interfaces in batteries: Advances from soft X-ray absorption spectroscopy to resonant inelastic scattering journal June 2018
Fingerprint Oxygen Redox Reactions in Batteries through High-Efficiency Mapping of Resonant Inelastic X-ray Scattering journal January 2019
Intergranular Cracking as a Major Cause of Long-Term Capacity Fading of Layered Cathodes journal May 2017
Bulk sensitive x-ray absorption spectroscopy free of self-absorption effects journal February 2011
Determination of the Kinetic Parameters of Mixed-Conducting Electrodes and Application to the System Li[sub 3]Sb journal January 1977
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
Mesoscale Chemomechanical Interplay of the LiNi 0.8 Co 0.15 Al 0.05 O 2 Cathode in Solid-State Polymer Batteries journal December 2018
Thermally driven mesoscale chemomechanical interplay in Li 0.5 Ni 0.6 Mn 0.2 Co 0.2 O 2 cathode materials journal January 2018
Visualization of O-O peroxo-like dimers in high-capacity layered oxides for Li-ion batteries journal December 2015
Elucidating anionic oxygen activity in lithium-rich layered oxides journal March 2018
Electrochemical Kinetics of the Li[Li 0.23 Co 0.3 Mn 0.47 ]O 2 Cathode Material Studied by GITT and EIS journal December 2010
Modification of Transition-Metal Redox by Interstitial Water in Hexacyanometalate Electrodes for Sodium-Ion Batteries journal December 2017
Utilizing Environmental Friendly Iron as a Substitution Element in Spinel Structured Cathode Materials for Safer High Energy Lithium-Ion Batteries journal December 2015
Chemomechanical interplay of layered cathode materials undergoing fast charging in lithium batteries journal November 2018
Coupling between oxygen redox and cation migration explains unusual electrochemistry in lithium-rich layered oxides journal December 2017
Disintegration of Meatball Electrodes for LiNi x Mn y Co z O2 Cathode Materials journal May 2017
Nanoscale Morphological and Chemical Changes of High Voltage Lithium–Manganese Rich NMC Composite Cathodes with Cycling journal July 2014
2 p x-ray absorption of 3 d transition-metal compounds: An atomic multiplet description including the crystal field journal September 1990
Temperature-Sensitive Structure Evolution of Lithium–Manganese-Rich Layered Oxides for Lithium-Ion Batteries journal October 2018
Identifying the Cause of Rupture of Li-Ion Batteries during Thermal Runaway journal October 2017
High-efficiency in situ resonant inelastic x-ray scattering (iRIXS) endstation at the Advanced Light Source journal March 2017
Depth-Dependent Redox Behavior of LiNi 0.6 Mn 0.2 Co 0.2 O 2 journal January 2018
In-operando high-speed tomography of lithium-ion batteries during thermal runaway journal April 2015
High‐Voltage Charging‐Induced Strain, Heterogeneity, and Micro‐Cracks in Secondary Particles of a Nickel‐Rich Layered Cathode Material journal March 2019
Phase Transformation and Lithiation Effect on Electronic Structure of Li x FePO 4 : An In-Depth Study by Soft X-ray and Simulations journal August 2012
Propagation topography of redox phase transformations in heterogeneous layered oxide cathode materials journal July 2018
Metal segregation in hierarchically structured cathode materials for high-energy lithium batteries journal January 2016
Oxygen redox chemistry without excess alkali-metal ions in Na2/3[Mg0.28Mn0.72]O2 journal January 2018
Quantification of Heterogeneous Degradation in Li‐Ion Batteries journal May 2019
Oxygen Release Induced Chemomechanical Breakdown of Layered Cathode Materials journal April 2018
Charge-compensation in 3d-transition-metal-oxide intercalation cathodes through the generation of localized electron holes on oxygen journal March 2016
Single-particle measurements of electrochemical kinetics in NMC and NCA cathodes for Li-ion batteries journal January 2018
Fundamental understanding and practical challenges of anionic redox activity in Li-ion batteries journal April 2018
Requirements for reversible extra-capacity in Li-rich layered oxides for Li-ion batteries journal January 2017
Correlating hysteresis and voltage fade in lithium- and manganese-rich layered transition-metal oxide electrodes journal August 2013

Cited By (5)

Using in situ and operando methods to characterize phase changes in charged lithium nickel cobalt aluminum oxide cathode materials journal January 2020
Spatial quantification of dynamic inter and intra particle crystallographic heterogeneities within lithium ion electrodes journal January 2020
TOPAS and TOPAS-Academic : an optimization program integrating computer algebra and crystallographic objects written in C++ journal February 2018
Spatial quantification of dynamic inter and intra particle crystallographic heterogeneities within lithium ion electrodes journal January 2020
Soft X-ray spectroscopy with transition-edge sensors at Stanford Synchrotron Radiation Lightsource beamline 10-1 journal November 2019

Similar Records

Related Subjects

25 ENERGY STORAGE