Skip to main content
U.S. Department of Energy
Office of Scientific and Technical Information

Impact of Microcrack Generation and Surface Degradation on a Nickel-Rich Layered Li[Ni0.9Co0.05Mn0.05]O2 Cathode for Lithium-Ion Batteries

Journal Article · · Chemistry of Materials
 [1];  [2]
  1. Univ. of Texas, Austin, TX (United States). Materials Science and Engineering Program and Texas Materials Institute; University of Texas at Austin
  2. Univ. of Texas, Austin, TX (United States). Materials Science and Engineering Program and Texas Materials Institute
In this work, to address the growing demand for energy density, the Ni-rich layered [Ni0.90Co0.05Mn0.05]O2 cathode has been synthesized and its electrochemical performance in lithium-ion cells has been benchmarked against a lower-Ni content Li[Ni0.6Co0.2Mn0.2]O2 cathode. Li[Ni0.90Co0.05Mn0.05]O2 delivers a high discharge capacity of 227 mA h g-1 compared to a capacity of 189 mA h g-1 for Li[Ni0.6Co0.2Mn0.2]O2 when cycled up to a lower cutoff voltage of 4.3 V, making it an appealing candidate for electric vehicles. With an increase in the charge cutoff voltage to 4.5 V, Li[Ni0.90Co0.05Mn0.05]O2 displays a capacity of 238 mA h g-1 compared to a capacity of 208 mA h g-1 for Li[Ni0.6Co0.2Mn0.2]O2. Although Li[Ni0.90Co0.05Mn0.05]O2 suffers during cycling from the usual rapid capacity fade in a manner similar to that of LiNiO2, 87 and 81% of the initial capacity could still be retained after 100 cycles even after cycling to higher cutoff voltages of 4.3 and 4.5 V, respectively. A comparison of Li[Ni0.90Co0.05Mn0.05]O2 and Li[Ni0.6Co0.2Mn0.2]O2 reveals that the capacity fade of Li[Ni0.90Co0.05Mn0.05]O2 originates largely from the anisotropic volume change and subsequent microcrack propagation in the bulk and NiO-like rock salt impurity phase formation on the particle surface, which are exacerbated at 4.5 V. Lastly, future work with appropriate doping and surface modification could improve further the performance of Li[Ni0.90Co0.05Mn0.05]O2.
Research Organization:
Univ. of Texas, Austin, TX (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
Grant/Contract Number:
EE0007762
OSTI ID:
1430488
Alternate ID(s):
OSTI ID: 2217288
Journal Information:
Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 19 Vol. 29; ISSN 0897-4756
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

References (33)

Beyond Intercalation-Based Li-Ion Batteries: The State of the Art and Challenges of Electrode Materials Reacting Through Conversion Reactions (Adv. Mater. 35/2010) journal September 2010
Observation of Microstructural Evolution in Li Battery Cathode Oxide Particles by In Situ Electron Microscopy journal May 2013
Compositionally Graded Cathode Material with Long-Term Cycling Stability for Electric Vehicles Application journal August 2016
LixCoO2 (0 journal June 1980
Structure and electrochemistry of lithium cobalt oxide synthesised at 400°C journal March 1992
In situ x-ray diffraction and electrochemical studies of Li1−xNiO2 journal December 1993
Relationship between non-stoichiometry and physical properties in LiNiO2 journal May 1995
Characterization and cathode performance of Li1 − xNi1 + xO2 prepared with the excess lithium method journal September 1995
Synthesis and properties of LiNiO2 as cathode material for secondary batteries journal April 1995
Performance of layered Li(Ni1/3Co1/3Mn1/3)O2 as cathode for Li-ion batteries journal November 2002
Comparison of the chemical stability of the high energy density cathodes of lithium-ion batteries journal November 2001
Surface changes on LiNi0.8Co0.2O2 particles during testing of high-power lithium-ion cells journal August 2002
Synthesis and structural characterization of layered Li[Ni1/3Co1/3Mn1/3]O2 cathode materials by ultrasonic spray pyrolysis method journal February 2004
Synthesis and electrochemical properties of Li[Ni0.8Co0.1Mn0.1]O2 and Li[Ni0.8Co0.2]O2 via co-precipitation journal September 2006
Thermal stability of Li1−yNixMn(1−x)/2Co(1−x)/2O2 layer-structured cathode materials used in Li-Ion batteries journal August 2011
Comparison of the structural and electrochemical properties of layered Li[NixCoyMnz]O2 (x = 1/3, 0.5, 0.6, 0.7, 0.8 and 0.85) cathode material for lithium-ion batteries journal July 2013
Capacity fading of LiAlyNi1−x−yCoxO2 cathode for lithium-ion batteries during accelerated calendar and cycle life tests (effect of depth of discharge in charge–discharge cycling on the suppression of the micro-crack generation of LiAlyNi1−x−yCoxO2 particle) journal August 2014
Anisotropic Lattice Strain and Mechanical Degradation of High- and Low-Nickel NCM Cathode Materials for Li-Ion Batteries journal February 2017
Effects of Chemical versus Electrochemical Delithiation on the Oxygen Evolution Reaction Activity of Nickel-Rich Layered Li M O 2 journal September 2015
Effect of Ni 2+ Content on Lithium/Nickel Disorder for Ni-Rich Cathode Materials journal April 2015
Role of Mn Content on the Electrochemical Properties of Nickel-Rich Layered LiNi 0.8– x Co 0.1 Mn 0.1+ x O 2 (0.0 ≤ x ≤ 0.08) Cathodes for Lithium-Ion Batteries journal March 2015
Structural Stability of LiNiO 2 Cycled above 4.2 V journal April 2017
Synthesis of Nanostructured Li[Ni 1/3 Co 1/3 Mn 1/3 ]O 2 via a Modified Carbonate Process journal January 2005
Progress in High-Capacity Core–Shell Cathode Materials for Rechargeable Lithium Batteries journal January 2014
Dynamic behaviour of interphases and its implication on high-energy-density cathode materials in lithium-ion batteries journal April 2017
Intrinsic Origins of Crack Generation in Ni-rich LiNi0.8Co0.1Mn0.1O2 Layered Oxide Cathode Material journal January 2017
Future generations of cathode materials: an automotive industry perspective journal January 2015
High-voltage positive electrode materials for lithium-ion batteries journal January 2017
High-energy-density lithium-ion battery using a carbon-nanotube–Si composite anode and a compositionally graded Li[Ni 0.85 Co 0.05 Mn 0.10 ]O 2 cathode journal January 2016
Phase Relationships and Structural and Chemical Stabilities of Charged Li[sub 1−x]CoO[sub 2−δ] and Li[sub 1−x]Ni[sub 0.85]Co[sub 0.15]O[sub 2−δ] Cathodes journal January 2003
Electrochemistry and Structural Chemistry of LiNiO[sub 2] (R3m) for 4 Volt Secondary Lithium Cells journal January 1993
Microstructural Changes in LiNi0.8Co0.15Al0.05O2 Positive Electrode Material during the First Cycle journal January 2011
Review—High-Capacity Li[Ni 1- x Co x /2 Mn x /2 ]O 2 ( x = 0.1, 0.05, 0) Cathodes for Next-Generation Li-Ion Battery journal January 2015

Cited By (28)

The Effects of Reversibility of H2-H3 Phase Transition on Ni-Rich Layered Oxide Cathode for High-Energy Lithium-Ion Batteries journal July 2019
Designation of a binocular structure for complex sources of x-rays and neutron source preprint January 2020
Simultaneously Dual Modification of Ni‐Rich Layered Oxide Cathode for High‐Energy Lithium‐Ion Batteries journal February 2019
High‐Voltage Charging‐Induced Strain, Heterogeneity, and Micro‐Cracks in Secondary Particles of a Nickel‐Rich Layered Cathode Material journal March 2019
Chemical, Structural, and Electronic Aspects of Formation and Degradation Behavior on Different Length Scales of Ni‐Rich NCM and Li‐Rich HE‐NCM Cathode Materials in Li‐Ion Batteries journal April 2019
Surface/Interface Structure Degradation of Ni‐Rich Layered Oxide Cathodes toward Lithium‐Ion Batteries: Fundamental Mechanisms and Remedying Strategies journal December 2019
Improved Cycling Stability of Li[Ni 0.90 Co 0.05 Mn 0.05 ]O 2 Through Microstructure Modification by Boron Doping for Li-Ion Batteries journal July 2018
Controllable Cathode–Electrolyte Interface of Li[Ni 0.8 Co 0.1 Mn 0.1 ]O 2 for Lithium Ion Batteries: A Review journal August 2019
3D Cube‐Maze‐Like Li‐Rich Layered Cathodes Assembled from 2D Porous Nanosheets for Enhanced Cycle Stability and Rate Capability of Lithium‐Ion Batteries journal December 2019
Hin und zurück – die Entwicklung von LiNiO 2 als Kathodenaktivmaterial journal May 2019
In‐Depth TEM Investigation on Structural Inhomogeneity within a Primary Li x Ni 0.835 Co 0.15 Al 0.015 O 2 Particle: Origin of Capacity Decay during High‐Rate Discharge journal November 2019
There and Back Again-The Journey of LiNiO 2 as a Cathode Active Material journal May 2019
In‐Depth TEM Investigation on Structural Inhomogeneity within a Primary Li x Ni 0.835 Co 0.15 Al 0.015 O 2 Particle: Origin of Capacity Decay during High‐Rate Discharge journal February 2020
Preparation, Lithium Storage Performance and Thermal Stability of Nickel-Rich Layered LiNi 0.815 Co 0.15 Al 0.035 O 2 /RGO Composites journal August 2018
New Insights for the Abuse Tolerance Behavior of LiMn 2 O 4 under High Cut‐Off Potential Conditions journal September 2018
Mechanistic understanding of intergranular cracking in NCM cathode material: mesoscale simulation with three-dimensional microstructure journal January 2018
Chemomechanical behaviors of layered cathode materials in alkali metal ion batteries journal January 2018
Single-crystal based studies for correlating the properties and high-voltage performance of Li[Ni x Mn y Co 1−x−y ]O 2 cathodes journal January 2019
Overall structural modification of a layered Ni-rich cathode for enhanced cycling stability and rate capability at high voltage journal January 2019
Indirect state-of-charge determination of all-solid-state battery cells by X-ray diffraction journal January 2019
Ni-Rich Oxide LiNi 0.85 Co 0.05 Mn 0.1 O 2 for Lithium Ion Battery: Effect of Microwave Radiation on Its Morphology and Electrochemical Property journal January 2019
Probing the Nature of Li + /Ni 2+ Disorder on the Structure and Electrochemical Performance in Ni-Based Layered Oxide Cathodes journal January 2019
Laboratory-Based X-ray Absorption Spectroscopy on a Working Pouch Cell Battery at Industrially-Relevant Charging Rates journal January 2019
The Role of Electrolyte in the First-Cycle Transformations of LiNi 0.6 Mn 0.2 Co 0.2 O 2 journal January 2019
Indirect state-of-charge determination of all-solid-state battery cells by X-ray diffraction text January 2019
Mechanism of Capacity Fading in the LiNi0.8Co0.1Mn0.1O2 Cathode Material for Lithium-Ion Batteries journal April 2019
Chemical, Structural, and Electronic Aspects of Formation and Degradation Behavior on Different Length Scales of Ni‐Rich NCM and Li‐Rich HE‐NCM Cathode Materials in Li‐Ion Batteries text January 2019
Indirect state-of-charge determination of all-solid-state battery cells by X-ray diffraction text January 2019