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

Title: Extending the Service Life of High–Ni Layered Oxides by Tuning the Electrode–Electrolyte Interphase

Journal Article · · Advanced Energy Materials

Abstract As a high‐energy‐density cathode for Li‐ion batteries, high‐Ni layered oxides, especially with ultrahigh Ni‐content, suffer from short lifespans, due in part to their unstable electrode–electrolyte interphase (EEI). Herein, the cycle life of LiNi 0.94 Co 0.06 O 2 is greatly extended by manipulating the EEI with a lithium bis(oxalate) (LiBOB) additive even when operated at a moderately high voltage (4.4 V vs Li/Li + ). Impressively, the capacity retention can be increased from 61 to 80% after 500 cycles in a full cell paired with a graphite anode. Additionally, the presence of LiBOB enables a robust boron‐ and oxygen‐enriched EEI that effectively inhibits continual electrolyte decomposition and offers a stable cathode surface. Moreover, the layered architecture of the cathode–electrolyte interphase (CEI) and the anode–electrolyte interphase (AEI) at the nanometer scale is revealed by time‐of‐flight secondary ion mass spectrometry. It is demonstrated that the cathode surface chemistry can significantly influence the AEI both chemically and physically, and AEI is modified from a thick “three‐layer” to a thin “two‐layer” architecture by tuning the cathode surface chemistry with LiBOB. This work presents a correlation between the EEI characteristics and battery performance and highlights the significance of manipulating surface chemistry in developing stable high‐energy‐density Li‐ion batteries.

Research Organization:
Univ. of Texas, Austin, TX (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO); USDOE
Grant/Contract Number:
EE0007762; DE‐EE0007762
OSTI ID:
2217319
Alternate ID(s):
OSTI ID: 1469243
Journal Information:
Advanced Energy Materials, Vol. 8, Issue 29; ISSN 1614-6832
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 145 works
Citation information provided by
Web of Science

References (59)

LiMOB, an Unsymmetrical Nonaromatic Orthoborate Salt for Nonaqueous Solution Electrochemical Applications journal January 2004
Electronic and Electrochemical Properties of Li 1– x Mn 1.5 Ni 0.5 O 4 Spinel Cathodes As a Function of Lithium Content and Cation Ordering journal October 2015
Mitigating Interfacial Potential Drop of Cathode–Solid Electrolyte via Ionic Conductor Layer To Enhance Interface Dynamics for Solid Batteries journal April 2018
Synthesis and Characterization of Lithium Bis(fluoromalonato)borate for Lithium-Ion Battery Applications journal November 2013
The Role of Cations on the Performance of Lithium Ion Batteries: A Quantitative Analytical Approach journal January 2018
Facilitating the Operation of Lithium-Ion Cells with High-Nickel Layered Oxide Cathodes with a Small Dose of Aluminum journal April 2018
Iodine-Doped Graphene with Opportune Interlayer Spacing as Superior Anode Materials for High-Performance Lithium-Ion Batteries journal July 2017
Surface reconstruction and chemical evolution of stoichiometric layered cathode materials for lithium-ion batteries journal March 2014
Mn(II) deposition on anodes and its effects on capacity fade in spinel lithium manganate–carbon systems journal September 2013
A Flexible Solid Electrolyte Interphase Layer for Long-Life Lithium Metal Anodes journal January 2018
Electrode materials for lithium secondary batteries with high energy densities journal August 2011
Unsymmetrical fluorinated malonatoborate as an amphoteric additive for high-energy-density lithium-ion batteries journal January 2018
Recent Advancements in Polymer-Based Composite Electrolytes for Rechargeable Lithium Batteries journal May 2018
Design of electrolyte solutions for Li and Li-ion batteries: a review journal November 2004
Electrode–Electrolyte Interface in Li-Ion Batteries: Current Understanding and New Insights journal October 2015
Materials Challenges and Opportunities of Lithium Ion Batteries journal January 2011
Suppressing Surface Lattice Oxygen Release of Li-Rich Cathode Materials via Heterostructured Spinel Li 4 Mn 5 O 12 Coating journal May 2018
Effect of Al 2 O 3 Coating on Stabilizing LiNi 0.4 Mn 0.4 Co 0.2 O 2 Cathodes journal August 2015
The Solid Electrolyte Interphase – The Most Important and the Least Understood Solid Electrolyte in Rechargeable Li Batteries journal December 2009
Characterization of Lithium Alkyl Carbonates by X-ray Photoelectron Spectroscopy: Experimental and Theoretical Study journal August 2005
Electrochemistry and Structural Chemistry of LiNiO[sub 2] (R3m) for 4 Volt Secondary Lithium Cells journal January 1993
Taming lithium metal through seeded growth journal January 2017
LiBOB as Electrolyte Salt or Additive for Lithium-Ion Batteries Based on LiNi[sub 0.8]Co[sub 0.15]Al[sub 0.05]O[sub 2]/Graphite journal January 2010
High-voltage positive electrode materials for lithium-ion batteries journal January 2017
Li 3 VO 4 anchored graphene nanosheets for long-life and high-rate lithium-ion batteries journal January 2015
Effectively suppressing dissolution of manganese from spinel lithium manganate via a nanoscale surface-doping approach journal December 2014
Mn versus Al in Layered Oxide Cathodes in Lithium-Ion Batteries: A Comprehensive Evaluation on Long-Term Cyclability journal February 2018
High-Capacity Cathode Material with High Voltage for Li-Ion Batteries journal January 2018
Lithiation-Derived Repellent toward Lithium Anode Safeguard in Quasi-solid Batteries journal February 2018
Kinetics of Lithium Ion Transfer at the Interface between Graphite and Liquid Electrolytes: Effects of Solvent and Surface Film journal November 2009
Dynamic formation of a solid-liquid electrolyte interphase and its consequences for hybrid-battery concepts journal March 2016
High-Rate Charging Induced Intermediate Phases and Structural Changes of Layer-Structured Cathode for Lithium-Ion Batteries journal August 2016
Formation and Inhibition of Metallic Lithium Microstructures in Lithium Batteries Driven by Chemical Crossover journal May 2017
Impact of Lithium Bis(oxalate)borate Electrolyte Additive on the Performance of High-Voltage Spinel/Graphite Li-Ion Batteries journal October 2013
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
An Outlook on Lithium Ion Battery Technology journal September 2017
The effect of electrolyte additives on electrochemical performance of silicon/mesoporous carbon (Si/MC) for anode materials for lithium-ion batteries journal September 2017
Challenges in the development of advanced Li-ion batteries: a review journal January 2011
Role of Lithium Salt on Solid Electrolyte Interface (SEI) Formation and Structure in Lithium Ion Batteries journal January 2014
Differentiating Contributions to “Ion Transfer” Barrier from Interphasial Resistance and Li + Desolvation at Electrolyte/Graphite Interface journal July 2010
Understanding the Degradation Mechanisms of LiNi 0.5 Co 0.2 Mn 0.3 O 2 Cathode Material in Lithium Ion Batteries journal August 2013
Intragranular cracking as a critical barrier for high-voltage usage of layer-structured cathode for lithium-ion batteries journal January 2017
Interfacial Mechanism in Lithium–Sulfur Batteries: How Salts Mediate the Structure Evolution and Dynamics journal June 2018
Growth of Adlayer Graphene on Cu Studied by Carbon Isotope Labeling journal January 2013
Precision Measurements of the Coulombic Efficiency of Lithium-Ion Batteries and of Electrode Materials for Lithium-Ion Batteries journal January 2010
High-Performance Heterostructured Cathodes for Lithium-Ion Batteries with a Ni-Rich Layered Oxide Core and a Li-Rich Layered Oxide Shell journal May 2016
Comparison of the Thermal Stability of Lithiated Graphite in LiBOB EC/DEC and in LiPF[sub 6] EC/DEC journal January 2003
Improved Electrochemical Performance of the 5 V Spinel Cathode LiMn[sub 1.5]Ni[sub 0.42]Zn[sub 0.08]O[sub 4] by Surface Modification journal January 2009
Chemical and structural instabilities of lithium ion battery cathodes journal September 2006
A highly stabilized nickel-rich cathode material by nanoscale epitaxy control for high-energy lithium-ion batteries journal January 2018
Chemical Analysis of Graphite/Electrolyte Interface Formed in LiBOB-Based Electrolytes journal January 2003
Promise and reality of post-lithium-ion batteries with high energy densities journal March 2016
Review on electrode–electrolyte solution interactions, related to cathode materials for Li-ion batteries journal March 2007
Dynamic behaviour of interphases and its implication on high-energy-density cathode materials in lithium-ion batteries journal April 2017
Electrochemical analysis for cycle performance and capacity fading of a lithium-ion battery cycled at elevated temperature journal October 2002
A perspective on nickel-rich layered oxide cathodes for lithium-ion batteries journal January 2017
Artificial solid-electrolyte interphase (SEI) for improved cycleability and safety of lithium–ion cells for EV applications journal September 2009
Effects of Imide–Orthoborate Dual-Salt Mixtures in Organic Carbonate Electrolytes on the Stability of Lithium Metal Batteries journal January 2018
In situ x-ray diffraction and electrochemical studies of Li1−xNiO2 journal December 1993