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

Essential effect of the electrolyte on the mechanical and chemical degradation of LiNi0.8Co0.15Al0.05O2 cathodes upon long-term cycling

Journal Article · · Journal of Materials Chemistry. A
DOI:https://doi.org/10.1039/d0ta07814j· OSTI ID:1775207
 [1];  [2];  [3];  [4];  [5];  [4];  [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS); Univ. of Kentucky, Lexington, KY (United States)
  3. Argonne National Lab. (ANL), Lemont, IL (United States)
  4. Univ. of Texas, Austin, TX (United States)
  5. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
+ Show Author Affiliations
Capacity fading during long-term cycling (>1500×) is still a critical challenge for Li-ion batteries that use Ni-rich layered oxides, e.g. LiNi0.8Co0.15Al0.05O2 (NCA), as the cathode. Microcracks have been previously recognized as one of the primary reasons for the observed capacity fade. Although there exists a generally developed mechanical understanding of microcracks, the role of the electrolyte has not been clearly understood, especially after extended cycling and at the atomic scale. Here, we unveil the microstructural evolution of spherical NCA secondary particles after long-term cycling using scanning transmission electron microscopy accompanied with electron energy loss spectroscopy. In this work, we found that the microcracks initiated and grew through grain boundaries, which then serve as the pathway for electrolyte penetration into secondary NCA particles. Additionally, the rock-salt phase reconstruction is prone to occur at the (003) surfaces of the primary particles or the crack surfaces, largely due to electrolyte (LiPF6 EC/EMC) corrosion. Crack propagation within the NCA grains is primarily a joint consequence from electrolyte corrosion and mechanical strain during lithiation/delithiation. During extended cycling, due to the distinctive surface facets, the primary grains located in the center of the secondary particles experience more intensive electrolyte corrosion, leading to a reduced contact with nearby particles, impairing the overall capacity. These results establish the initiation and growth mechanism of microcracks and voids in NCA-based cathodes during cycling and point out the role of the electrolyte in affecting the degradation of NCA-based cathodes.
Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)
Sponsoring Organization:
USDOE; USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division
Grant/Contract Number:
AC02-06CH11357; AC05-00OR22725; EE0007762
OSTI ID:
1775207
Alternate ID(s):
OSTI ID: 1809085
OSTI ID: 1762512
Journal Information:
Journal of Materials Chemistry. A, Journal Name: Journal of Materials Chemistry. A Journal Issue: 4 Vol. 9; ISSN 2050-7488
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

References (42)

Enhancing Interfacial Bonding between Anisotropically Oriented Grains Using a Glue-Nanofiller for Advanced Li-Ion Battery Cathode journal April 2016
Observation of Microstructural Evolution in Li Battery Cathode Oxide Particles by In Situ Electron Microscopy journal May 2013
Narrowing the Gap between Theoretical and Practical Capacities in Li-Ion Layered Oxide Cathode Materials journal July 2017
From Surface ZrO 2 Coating to Bulk Zr Doping by High Temperature Annealing of Nickel-Rich Lithiated Oxides and Their Enhanced Electrochemical Performance in Lithium Ion Batteries journal September 2017
Mn versus Al in Layered Oxide Cathodes in Lithium-Ion Batteries: A Comprehensive Evaluation on Long-Term Cyclability journal February 2018
Oxygen Release Degradation in Li‐Ion Battery Cathode Materials: Mechanisms and Mitigating Approaches journal April 2019
Cobalt dissolution in LiCoO2-based non-aqueous rechargeable batteries journal January 1996
Review of selected electrode–solution interactions which determine the performance of Li and Li ion batteries journal August 2000
Surface changes on LiNi0.8Co0.2O2 particles during testing of high-power lithium-ion cells journal August 2002
The preparation and role of Li2ZrO3 surface coating LiNi0.5Co0.2Mn0.3O2 as cathode for lithium-ion batteries journal January 2016
Reprint of “Studies of local degradation phenomena in composite cathodes for lithium-ion batteries” journal December 2007
Improvement of long-term cycling performance of Li[Ni0.8Co0.15Al0.05]O2 by AlF3 coating journal July 2013
Role of V2O5 coating on LiNiO2-based materials for lithium ion battery journal January 2014
Capacity fade of LiAlyNi1−x−yCoxO2 cathode for lithium-ion batteries during accelerated calendar and cycle life tests (surface analysis of LiAlyNi1−x−yCoxO2 cathode after cycle tests in restricted depth of discharge ranges) journal July 2014
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
Control of electrochemical properties of nickel-rich layered cathode materials for lithium ion batteries by variation of the manganese to cobalt ratio journal February 2015
Microstructural study on degradation mechanism of layered LiNi0.6Co0.2Mn0.2O2 cathode materials by analytical transmission electron microscopy journal March 2016
Insights into the inner structure of high-nickel agglomerate as high-performance lithium-ion cathodes journal November 2016
Capacity Fading of Ni-Rich Li[Ni x Co y Mn 1– x – y ]O 2 (0.6 ≤ x ≤ 0.95) Cathodes for High-Energy-Density Lithium-Ion Batteries: Bulk or Surface Degradation? journal January 2018
A New Coating Method for Alleviating Surface Degradation of LiNi 0.6 Co 0.2 Mn 0.2 O 2 Cathode Material: Nanoscale Surface Treatment of Primary Particles journal February 2015
Intergranular Cracking as a Major Cause of Long-Term Capacity Fading of Layered Cathodes journal May 2017
Oxygen Release Induced Chemomechanical Breakdown of Layered Cathode Materials journal April 2018
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
Correlating Structural Changes and Gas Evolution during the Thermal Decomposition of Charged Li x Ni 0.8 Co 0.15 Al 0.05 O 2 Cathode Materials journal January 2013
Investigation of Changes in the Surface Structure of Li x Ni 0.8 Co 0.15 Al 0.05 O 2 Cathode Materials Induced by the Initial Charge journal December 2013
Electron Spectroscopy Study of Li[Ni,Co,Mn]O 2 /Electrolyte Interface: Electronic Structure, Interface Composition, and Device Implications journal April 2015
Lithium Batteries and Cathode Materials journal October 2004
Kinetics Tuning of Li-Ion Diffusion in Layered Li(Ni x Mn y Co z )O 2 journal June 2015
Development of Microstrain in Aged Lithium Transition Metal Oxides journal June 2014
In situ click chemistry generation of cyclooxygenase-2 inhibitors journal February 2017
Structural absorption by barbule microstructures of super black bird of paradise feathers journal January 2018
Tailoring grain boundary structures and chemistry of Ni-rich layered cathodes for enhanced cycle stability of lithium-ion batteries journal June 2018
In situ soft XAS study on nickel-based layered cathode material at elevated temperatures: A novel approach to study thermal stability journal October 2014
Intrinsic Origins of Crack Generation in Ni-rich LiNi0.8Co0.1Mn0.1O2 Layered Oxide Cathode Material journal January 2017
Intrinsic origin of intra-granular cracking in Ni-rich layered oxide cathode materials journal January 2018
Dual functions of zirconium modification on improving the electrochemical performance of Ni-rich LiNi 0.8 Co 0.1 Mn 0.1 O 2 journal January 2018
Electrical energy storage for transportation—approaching the limits of, and going beyond, lithium-ion batteries journal January 2012
Significant Improvement of Electrochemical Performance of AlF3-Coated Li[Ni0.8Co0.1Mn0.1]O2 Cathode Materials journal January 2007
Capacity-Fading Mechanisms of LiNiO[sub 2]-Based Lithium-Ion Batteries journal January 2009
Microstructural Changes in LiNi0.8Co0.15Al0.05O2 Positive Electrode Material during the First Cycle journal January 2011
Morphological and Structural Changes of Mg-Substituted Li(Ni,Co,Al)O2 during Overcharge Reaction journal January 2011
A Study of Li-Ion Cells Operated to 4.5 V and at 55°C journal January 2016

Similar Records

Boosting Cell Performance of LiNi0.8Co0.15A0.05O2 via Surface Structure Design
Journal Article · Tue Nov 12 19:00:00 EST 2019 · Small · OSTI ID:1602539
Evolution of the Electrode–Electrolyte Interface of LiNi0.8Co0.15Al0.05O2 Electrodes Due to Electrochemical and Thermal Stress
Journal Article · Tue Jan 09 19:00:00 EST 2018 · Chemistry of Materials · OSTI ID:1470192

Related Subjects

25 ENERGY STORAGE