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

Title: Understanding the Origins of Higher Capacities at Faster Rates in Lithium-Excess LixNi2–4x/3Sbx/3O2

Journal Article · · Chemistry of Materials
ORCiD logo [1];  [2];  [3];  [4];  [5];  [6];  [2];  [7]
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
  2. Technische Univ. Munchen, Garching (Germany)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
  4. Paul Scherrer Inst. (PSI), Villigen (Switzerland)
  5. Harvard Univ., Cambridge, MA (United States)
  6. Georgia Inst. of Technology, Atlanta, GA (United States)
  7. Univ. of California, Berkeley, CA (United States)
+ Show Author Affiliations

Here, the lithium-excess LixNi2-4x/3Sbx/3O2 (LNSO) materials were previously shown to demonstrate higher capacities and improved cyclability with increasing lithium content. While the performance trend is promising, observed capacities are much lower than theoretical capacities, pointing to a need for further understanding of active redox processes in these materials. In this work, we study the electrochemical behavior of the LNSO materials as a function of lithium content and at slow and fast rates. Surprisingly, Li1.15Ni0.47Sb0.38O2 (LNSO-15) exhibits higher discharge capacities at faster rates and traverses distinct voltage curves at slow and fast rates. To understand these two peculiarities, we characterize the redox activity of nickel, antimony, and oxygen at different rates. While experiments confirm some nickel redox activity and oxygen loss, these two mechanisms cannot account for all observed capacity. We propose that the balance of the observed capacity may be due reversible oxygen redox and that the rate-dependent voltage curve features may derive from irreversible nickel migration occurring on slow charge. As future high energy density cathodes are likely to contain both lithium excess and high nickel content, both of these findings have important implications for the development of novel high capacity cathode materials.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
Grant/Contract Number:
AC02-05CH11231; AC02-06CH11357
OSTI ID:
1476471
Alternate ID(s):
OSTI ID: 1374886
Journal Information:
Chemistry of Materials, Vol. 29, Issue 6; Related Information: © 2017 American Chemical Society.; ISSN 0897-4756
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 16 works
Citation information provided by
Web of Science

References (62)

High-Energy Cathode Materials (Li 2 MnO 3 –LiMO 2 ) for Lithium-Ion Batteries journal March 2013
Unlocking the Potential of Cation-Disordered Oxides for Rechargeable Lithium Batteries journal January 2014
The significance of the Li2MnO3 component in ‘composite’ xLi2MnO3·(1−x)LiMn0.5Ni0.5O2 electrodes journal October 2004
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
Advances in manganese-oxide ‘composite’ electrodes for lithium-ion batteries
  • Thackeray, Michael M.; Johnson, Christopher S.; Vaughey, John T.
  • Journal of Materials Chemistry, Vol. 15, Issue 23, p. 2257-2267 https://doi.org/10.1039/b417616m
journal March 2005
Li2MnO3-stabilized LiMO2 (M = Mn, Ni, Co) electrodes for lithium-ion batteries journal January 2007
Electrochemical kinetics of the 0.5Li2MnO3·0.5LiMn0.42Ni0.42Co0.16O2 ‘composite’ layered cathode material for lithium-ion batteries journal January 2012
Kinetics Study of the High Potential Range of Lithium-Rich Transition-Metal Oxides for Lithium-Ion Batteries by Electrochemical Methods journal January 2010
Enhancing the rate capability of high capacity xLi2MnO3 · (1−x)LiMO2 (M=Mn, Ni, Co) electrodes by Li–Ni–PO4 treatment journal April 2009
Understanding the Rate Capability of High-Energy-Density Li-Rich Layered Li 1.2 Ni 0.15 Co 0.1 Mn 0.55 O 2 Cathode Materials journal December 2013
Microstructural Changes in LiNi0.8Co0.15Al0.05O2 Positive Electrode Material during the First Cycle journal January 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
First Evidence of Manganese–Nickel Segregation and Densification upon Cycling in Li-Rich Layered Oxides for Lithium Batteries journal July 2013
The Configurational Space of Rocksalt-Type Oxides for High-Capacity Lithium Battery Electrodes journal May 2014
Designing New Lithium-Excess Cathode Materials from Percolation Theory: Nanohighways in Li x Ni 2–4 x /3 Sb x /3 O 2 journal December 2014
A Novel On-Line Mass Spectrometer Design for the Study of Multiple Charging Cycles of a Li-O 2 Battery journal January 2013
The Effect of Water on the Discharge Capacity of a Non-Catalyzed Carbon Cathode for Li-O2 Batteries journal January 2012
Anodic Oxidation of Conductive Carbon and Ethylene Carbonate in High-Voltage Li-Ion Batteries Quantified by On-Line Electrochemical Mass Spectrometry journal January 2015
High-capacity lithium insertion materials of lithium nickel manganese oxides for advanced lithium-ion batteries: toward rechargeable capacity more than 300 mA h g−1 journal January 2011
White lines and d -band occupancy for the 3 d transition-metal oxides and lithium transition-metal oxides journal June 2004
Mechanisms Associated with the “Plateau” Observed at High Voltage for the Overlithiated Li 1.12 (Ni 0.425 Mn 0.425 Co 0.15 ) 0.88 O 2 System journal August 2008
Direct observation of the partial formation of a framework structure for Li-rich layered cathode material Li[Ni0.17Li0.2Co0.07Mn0.56]O2 upon the first charge and discharge journal May 2011
Investigation of the Irreversible Capacity Loss in the Lithium-Rich Oxide Li[Li1/5Ni1/5Mn3/5]O2 journal January 2011
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
Structural Changes in Li 2 MnO 3 Cathode Material for Li-Ion Batteries journal December 2013
A Li-Rich Layered Cathode Material with Enhanced Structural Stability and Rate Capability for Li-on Batteries journal December 2013
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
In Situ X-Ray Absorption Study of a Layered Manganese-Chromium Oxide-Based Cathode Material journal January 2002
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
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
In Situ and Ex Situ XRD Investigation of Li[Cr[sub x]Li[sub 1/3−x/3]Mn[sub 2/3−2x/3]]O[sub 2] (x=1/3) Cathode Material journal January 2003
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
Demonstrating Oxygen Loss and Associated Structural Reorganization in the Lithium Battery Cathode Li[Ni0.2Li0.2Mn0.6]O2 journal June 2006
Direct evidence of oxygen evolution from Li1+x (Ni1/3Mn1/3Co1/3)1−x O2 at high potentials journal February 2008
Quantification of Oxygen Loss from Li[sub 1+x](Ni[sub 1/3]Mn[sub 1/3]Co[sub 1/3])[sub 1−x]O[sub 2] at High Potentials by Differential Electrochemical Mass Spectrometry journal January 2009
Reversible anionic redox chemistry in high-capacity layered-oxide electrodes journal July 2013
Activation Mechanism of LiNi 0.80 Co 0.15 Al 0.05 O 2 : Surface and Bulk Operando Electrochemical, Differential Electrochemical Mass Spectrometry, and X-ray Diffraction Analyses journal January 2015
Critical Role of Oxygen Evolved from Layered Li–Excess Metal Oxides in Lithium Rechargeable Batteries journal July 2012
Differential Electrochemical Mass Spectrometry Study of the Interface of x Li 2 MnO 3 ·(1– x )LiMO 2 (M = Ni, Co, and Mn) Material as a Positive Electrode in Li-Ion Batteries journal August 2014
Charge-compensation in 3d-transition-metal-oxide intercalation cathodes through the generation of localized electron holes on oxygen journal March 2016
CO 2 and O 2 Evolution at High Voltage Cathode Materials of Li-Ion Batteries: A Differential Electrochemical Mass Spectrometry Study journal June 2014
Oxidative Electrolyte Solvent Degradation in Lithium-Ion Batteries: An In Situ Differential Electrochemical Mass Spectrometry Investigation journal January 1999
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
High-energy ‘composite’ layered manganese-rich cathode materials via controlling Li2MnO3 phase activation for lithium-ion batteries journal January 2012
Solvents’ Critical Role in Nonaqueous Lithium–Oxygen Battery Electrochemistry journal May 2011
The structural and chemical origin of the oxygen redox activity in layered and cation-disordered Li-excess cathode materials journal May 2016
High Performance Li 2 Ru 1– y Mn y O 3 (0.2 ≤ y ≤ 0.8) Cathode Materials for Rechargeable Lithium-Ion Batteries: Their Understanding journal March 2013
Understanding the Roles of Anionic Redox and Oxygen Release during Electrochemical Cycling of Lithium-Rich Layered Li 4 FeSbO 6 journal April 2015
A new class of high capacity cation-disordered oxides for rechargeable lithium batteries: Li–Ni–Ti–Mo oxides journal January 2015
The relationship between the composition of lithium nickel oxide and the loss of reversibility during the first cycle journal June 1996
Effect of High Voltage on the Structure and Electrochemistry of LiNi 0.5 Mn 0.5 O 2 :  A Joint Experimental and Theoretical Study journal October 2006
Role of Electronic Structure in the Susceptibility of Metastable Transition-Metal Oxide Structures to Transformation journal October 2004
Synthesis and electrochemical properties of layered LiNi2/3Sb1/3O2 journal November 2007
Structure and electrochemistry of Li1±yNiO2 and a new Li2NiO2 phase with the Ni (OH)2 structure journal December 1990
Layered Lithium Insertion Material of LiNi 1/2 Mn 1/2 O 2 : A Possible Alternative to LiCoO 2 for Advanced Lithium-Ion Batteries journal August 2001
Layered Li[Ni[sub x]Co[sub 1−2x]Mn[sub x]]O[sub 2] Cathode Materials for Lithium-Ion Batteries journal January 2001
Designing High-Capacity, Lithium-Ion Cathodes Using X-ray Absorption Spectroscopy journal December 2011
Li de-intercalation mechanism in LiNiMnO cathode material for Li-ion batteries journal March 2005
Factors that affect Li mobility in layered lithium transition metal oxides journal September 2006
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
Influence of Cationic Substitutions on the Oxygen Loss and Reversible Capacity of Lithium-Rich Layered Oxide Cathodes journal March 2011
Optimization of the Composition of the Li[sub 1−z]Ni[sub 1+z]O[sub 2] Electrode Materials: Structural, Magnetic, and Electrochemical Studies journal January 1996

Cited By (2)

Possible high-potential ilmenite type N a 1 M O 3   ( M = V – Ni ) cathodes realized by dominant oxygen redox reaction journal January 2020
Sb-based electrode materials for rechargeable batteries journal January 2018

Similar Records

Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY