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

Title: Raman microscopy of lithium-manganese-rich transition metal oxide cathodes

Journal Article · · Journal of the Electrochemical Society
DOI:https://doi.org/10.1149/2.0361501jes· OSTI ID:1185646
 [1];  [2];  [1];  [3];  [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division
  2. Tennessee Technological Univ., Cookeville, TN (United States). Dept. of Chemistry
  3. Indian Inst. of Technology, Telangana (India)

Lithium-rich and manganese-rich (LMR) layered transition metal (TM) oxide composites with general formula xLi2MnO3·(1-x)LiMO2 (M = Ni, Co, Mn) are promising cathode candidates for high energy density lithium ion batteries. Lithium-manganese-rich TM oxides crystallize as a nanocomposite layered phase whose structure further evolves with electrochemical cycling. Raman spectroscopy is a powerful tool to monitor the crystal chemistry and correlate phase changes with electrochemical behavior. While several groups have reported Raman spectra of lithium rich TM oxides, the data show considerable variability in terms of both the vibrational features observed and their interpretation. In this paper, Raman microscopy is used to investigate lithium-rich and manganese-rich TM cathodes as a function of voltage and electrochemical cycling at various temperatures. No growth of a spinel phase is observed within the cycling conditions. However, analysis of the Raman spectra does indicate the structure of LMR-NMC deviates significantly from an ideal layered phase. Finally, the results also highlight the importance of using low laser power and large sample sizes to obtain consistent data sets.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Vehicle Technologies Office. Batteries for Advanced Transportation Technologies (BATT) Program
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
1185646
Journal Information:
Journal of the Electrochemical Society, Vol. 162, Issue 1; ISSN 0013-4651
Publisher:
The Electrochemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 113 works
Citation information provided by
Web of Science

References (58)

6Li MAS NMR and in situ X-ray studies of lithium nickel manganese oxides journal June 2003
Coexistence of layered and cubic rocksalt structures with a common oxygen sublattice in Li1.2Mn0.4Fe0.4O2 particles: A transmission electron microscopy study journal May 2008
Long-Range and Local Structure in the Layered Oxide Li 1.2 Co 0.4 Mn 0.4 O 2 journal April 2011
Evolutions of Li 1.2 Mn 0.61 Ni 0.18 Mg 0.01 O 2 during the Initial Charge/Discharge Cycle Studied by Advanced Electron Microscopy journal September 2012
Direct Atomic-Resolution Observation of Two Phases in the Li 1.2 Mn 0.567 Ni 0.166 Co 0.067 O 2 Cathode Material for Lithium-Ion Batteries 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
Li2MnO3-stabilized LiMO2 (M = Mn, Ni, Co) electrodes for lithium-ion batteries journal January 2007
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
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 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
Mechanism of Electrochemical Activity in Li 2 MnO 3 journal May 2003
Overcapacity of Li[Ni[sub x]Li[sub 1/3−2x/3]Mn[sub 2/3−x/3]]O[sub 2] Electrodes journal January 2004
Structural Changes in Li 2 MnO 3 Cathode Material for Li-Ion Batteries journal December 2013
Voltage Fade of Layered Oxides: Its Measurement and Impact on Energy Density journal January 2013
Correlating hysteresis and voltage fade in lithium- and manganese-rich layered transition-metal oxide electrodes journal August 2013
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
High-energy ‘composite’ layered manganese-rich cathode materials via controlling Li2MnO3 phase activation for lithium-ion batteries journal January 2012
In situ Raman spectroscopy of layered solid solution Li2MnO3–LiMO2 (M = Ni, Mn, Co) journal November 2012
Examining Hysteresis in Composite x Li 2 MnO 3 ·(1– x )LiMO 2 Cathode Structures journal March 2013
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
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
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
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
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
Layered (1−x−y)LiNi[sub 1/2]Mn[sub 1/2]O[sub 2]⋅xLi[Li[sub 1/3]Mn[sub 2/3]] O[sub 2]⋅yLiCoO[sub 2] (0≤x=y≤0.3 and x+y=0.5) Cathode Materials journal January 2005
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
Integrated Materials xLi[sub 2]MnO[sub 3]⋅(1−x)LiMn[sub 1/3]Ni[sub 1/3]Co[sub 1/3]O[sub 2] (x=0.3, 0.5, 0.7) Synthesized journal January 2010
Li 1.20 Mn 0.54 Co 0.13 Ni 0.13 O 2 with Different Particle Sizes as Attractive Positive Electrode Materials for Lithium-Ion Batteries: Insights into Their Structure journal June 2012
Study of the Lithium-Rich Integrated Compound xLi 2 MnO 3 ·(1-x)LiMO 2 (x around 0.5; M = Mn, Ni, Co; 2:2:1) and Its Electrochemical Activity as Positive Electrode in Lithium Cells journal December 2012
Ex situ and in situ Raman microscopic investigation of the differences between stoichiometric LiMO2 and high-energy xLi2MnO3·(1–x)LiMO2 (M = Ni, Co, Mn) journal June 2014
Raman Microspectrometry Applied to the Study of Electrode Materials for Lithium Batteries journal March 2010
Local State-of-Charge Mapping of Lithium-Ion Battery Electrodes journal July 2011
Surface studies of high voltage lithium rich composition: Li1.2Mn0.525Ni0.175Co0.1O2 journal October 2012
Electrochemical and rate performance study of high-voltage lithium-rich composition: Li1.2Mn0.525Ni0.175Co0.1O2 journal February 2012
Lattice vibrations of materials for lithium rechargeable batteries III. Lithium manganese oxides journal June 2003
Local structure of lithiated manganese oxides journal January 2006
Lithium intercalated compounds journal January 2003
Vibrational spectroscopic and electrochemical studies of the low and high temperature phases of LiCo1−x MxO2 (M = Ni or Ti) journal July 1996
Physical Properties and Electrochemical Features of Lithium Nickel-Cobalt Oxide Cathode Materials Prepared at Moderate Temperature journal January 1999
Relationship between Chemical Bonding Character and Electrochemical Performance in Nickel-Substituted Lithium Manganese Oxides journal May 2001
Study of the surface modification of LiNi1/3Co1/3Mn1/3O2 cathode material for lithium ion battery journal October 2011
Synthesis, Characterization and Electrochemistry of Lithium Battery Electrodes: x Li 2 MnO 3 ·(1 − x )LiMn 0.333 Ni 0.333 Co 0.333 O 2 (0 ≤ x ≤ 0.7) journal October 2008
Spectroscopic studies of the local structure in positive electrodes for lithium batteries journal July 2002
Lithium and Deuterium NMR Studies of Acid-Leached Layered Lithium Manganese Oxides journal December 2002
Characterization and Electrocatalytic Behavior of Layered Li 2 MnO 3 and Its Acid-Treated Form journal January 2007
Atomic Structure of Li 2 MnO 3 after Partial Delithiation and Re-Lithiation journal June 2013
Electrochemical activation of Li2MnO3 at elevated temperature investigated by in situ Raman microscopy journal October 2013
Understanding Long-Term Cycling Performance of Li 1.2 Ni 0.15 Mn 0.55 Co 0.1 O 2 –Graphite Lithium-Ion Cells journal January 2013
Countering the Voltage Decay in High Capacity xLi 2 MnO 3 •(1–x)LiMO 2 Electrodes (M=Mn, Ni, Co) for Li + -Ion Batteries journal January 2012
Mitigation of Layered to Spinel Conversion of a Li-Rich Layered Metal Oxide Cathode Material for Li-Ion Batteries journal December 2013
Probing Thermally Induced Decomposition of Delithiated Li 1.2– x Ni 0.15 Mn 0.55 Co 0.1 O 2 by in Situ High-Energy X-ray Diffraction journal July 2014
Interpretation of Raman spectra of disordered and amorphous carbon journal May 2000
Electrochemical activity of carbon blacks in LiPF6-based organic electrolytes journal January 2014
Nanoscale Morphological and Chemical Changes of High Voltage Lithium–Manganese Rich NMC Composite Cathodes with Cycling journal July 2014
Effect of Synthesis Conditions on the First Charge and Reversible Capacities of Lithium-Rich Layered Oxide Cathodes journal July 2013
Mechanism of Electrochemical Activity in Li2MnO3. journal August 2003
Direct Atomic-Resolution Observation of Two Phases in the Li 1.2 Mn 0.567 Ni 0.166 Co 0.067 O 2 Cathode Material for Lithium-Ion Batteries journal April 2013

Cited By (17)

Composition and Impedance Heterogeneity in Oxide Electrode Cross-Sections Detected by Raman Spectroscopy journal February 2018
Phase Transformation of Lithium‐rich Oxide Cathode in Full Cell and its Suppression by Solid Electrolyte Interphase on Graphite Anode journal March 2020
Applications of Conventional Vibrational Spectroscopic Methods for Batteries Beyond Li-Ion journal March 2018
Toward Low-Cost, High-Energy Density, and High-Power Density Lithium-Ion Batteries journal June 2017
Charge-compensation in 3d-transition-metal-oxide intercalation cathodes through the generation of localized electron holes on oxygen journal March 2016
Manganese oxidation as the origin of the anomalous capacity of Mn-containing Li-excess cathode materials journal July 2019
Effective use of an idle carbon-deposited catalyst for energy storage applications journal January 2016
Role of polyvinylpyrrolidone in the electrochemical performance of Li 2 MnO 3 cathode for lithium-ion batteries journal January 2019
High rate hybrid MnO 2 @CNT fabric anodes for Li-ion batteries: properties and a lithium storage mechanism study by in situ synchrotron X-ray scattering journal January 2019
Carbon fibre paper coated by a layered manganese oxide: a nano-structured electrocatalyst for water-oxidation with high activity over a very wide pH range journal January 2019
Multiscale modeling and characterization for performance and safety of lithium-ion batteries journal August 2015
Low resistance at LiNi 1/3 Mn 1/3 Co 1/3 O 2 and Li 3 PO 4 interfaces journal February 2020
Physico-chemistry of energy-dense Li 1.2 Mn 0.52 Co 0.13 Ni 0.13 Al 0.02 O 2 cathode material for lithium-ion batteries obtained from urea and ethylene glycol fuels journal September 2019
Effect of Potassium Doping on the Electrochemical Properties of 0.5Li 2 MnO 3 -0.5LiMn 0.375 Ni 0.375 Co 0.25 O 2 Cathode journal January 2018
Suppression of Voltage Decay and Improvement in Electrochemical Performance by Zirconium Doping in Li-Rich Cathode Materials for Li-Ion Batteries journal January 2018
Carbon fibre paper coated by a layered manganese oxide: a nano-structured electrocatalyst for water-oxidation with high activity over a very wide pH range text January 2019
High Rate Hybrid MnO2@CNT Fabric Anode for Li-Ion Batteries: Properties and Lithium Storage Mechanism by In-Situ Synchrotron X-Ray Scattering text January 2020