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Title: Surface Chemistry Dependence on Aluminum Doping in Ni-rich LiNi0.8Co0.2-yAlyO2 Cathodes

Journal Article · · Scientific Reports
 [1];  [2];  [3];  [1];  [4];  [4];  [4];  [4];  [1];  [3];  [3];  [3];  [5];  [2];  [1]
  1. Binghamton Univ., NY (United States)
  2. Univ. of Cambridge (United Kingdom)
  3. Rutgers Univ., North Brunswick, NJ (United States)
  4. Scienta Omicron AB, Uppsala (Sweden)
  5. Diamond Light Source Ltd., Oxfordshire (United Kingdom)
+ Show Author Affiliations

Aluminum is a common dopant across oxide cathodes for improving the bulk and cathode-electrolyte interface (CEI) stability. Aluminum in the bulk is known to enhance structural and thermal stability, yet the exact influence of aluminum at the CEI remains unclear. To address this, we utilized a combination of X-ray photoelectron and absorption spectroscopy to identify aluminum surface environments and extent of transition metal reduction for Ni-rich LiNi0.8Co0.2-yAlyO2 (0%, 5%, or 20% Al) layered oxide cathodes tested at 4.75 V under thermal stress (60 °C). For these tests, we compared the conventional LiPF6 salt with the more thermally stable LiBF4 salt. The CEI layers are inherently different between these two electrolyte salts, particularly for the highest level of Al-doping (20%) where a thicker (thinner) CEI layer is found for LiPF6 (LiBF4). Focusing on the aluminum environment, we reveal the type of surface aluminum species are dependent on the electrolyte salt, as Al-O-F- and Al-F-like species form when using LiPF6 and LiBF4, respectively. In both cases, we find cathode-electrolyte reactions drive the formation of a protective Al-F-like barrier at the CEI in Al-doped oxide cathodes.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Northeastern Center for Chemical Energy Storage (NECCES); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
Grant/Contract Number:
AC02-05CH11231; SC0012583
OSTI ID:
1591835
Journal Information:
Scientific Reports, Journal Name: Scientific Reports Journal Issue: 1 Vol. 9; ISSN 2045-2322
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English

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Short-Range Order and Unusual Modes of Nickel Redox in a Fluorine-Substituted Disordered Rocksalt Oxide Lithium-Ion Cathode journal September 2018
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Isotropic High Field NMR Spectra of Li-Ion Battery Materials with Anisotropy >1 MHz journal January 2012
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A Combined Solid-State NMR and Diffraction Study of the Structures and Acidity of Fluorinated Aluminas:  Implications for Catalysis journal August 2003
Surface reconstruction and chemical evolution of stoichiometric layered cathode materials for lithium-ion batteries journal March 2014
Metal segregation in hierarchically structured cathode materials for high-energy lithium batteries journal January 2016
High-energy cathode material for long-life and safe lithium batteries journal March 2009
Evolution of redox couples in Li- and Mn-rich cathode materials and mitigation of voltage fade by reducing oxygen release journal July 2018
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Thermal Stability of Electrolytes with Mixtures of LiPF[sub 6] and LiBF[sub 4] Used in Lithium-Ion Cells journal January 2004
Oxygen Release and Its Effect on the Cycling Stability of LiNi x Mn y Co z O 2 (NMC) Cathode Materials for Li-Ion Batteries journal January 2017
Surface Structure and High-Voltage Charge/Discharge Characteristics of Al-Oxide Coated LiNi 1/3 Co 1/3 Mn 1/3 O 2 Cathodes journal January 2015
Editors' Choice—Growth of Ambient Induced Surface Impurity Species on Layered Positive Electrode Materials and Impact on Electrochemical Performance journal January 2017
A Study of Li-Ion Cells Operated to 4.5 V and at 55°C journal January 2016
A Comprehensive Analysis of the Interphasial and Structural Evolution over Long‐Term Cycling of Ultrahigh‐Nickel Cathodes in Lithium‐Ion Batteries journal October 2019
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Cobalt dissolution in LiCoO2-based non-aqueous rechargeable batteries journal January 1996
Effects of Al doping on the microstructure of LiCoO2 cathode materials journal January 2001
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An update on the high temperature ageing mechanism in LiMn2O4-based Li-ion cells journal September 1999
Surface chemistry of metal oxide coated lithium manganese nickel oxide thin film cathodes studied by XPS journal February 2013
Spectroscopic characterization of crystalline AlF3 phases journal January 2010
Aluminum-doped lithium nickel cobalt oxide electrodes for high-power lithium-ion batteries journal April 2004
Correlation between dissolution behavior and electrochemical cycling performance for LiNi1/3Co1/3Mn1/3O2-based cells journal June 2012
Improvement of long-term cycling performance of Li[Ni0.8Co0.15Al0.05]O2 by AlF3 coating journal July 2013
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Evolution of the Electrode–Electrolyte Interface of LiNi 0.8 Co 0.15 Al 0.05 O 2 Electrodes Due to Electrochemical and Thermal Stress journal January 2018
Phase Evolution and Degradation Modes of R 3̅ m Li x Ni 1– y – z Co y Al z O 2 Electrodes Cycled Near Complete Delithiation journal October 2018
Short-Range Order and Unusual Modes of Nickel Redox in a Fluorine-Substituted Disordered Rocksalt Oxide Lithium-Ion Cathode journal September 2018
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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
Mechanisms of LiCoO 2 Cathode Degradation by Reaction with HF and Protection by Thin Oxide Coatings journal October 2015
Direct Observation of Lattice Aluminum Environments in Li Ion Cathodes LiNi 1– y – z Co y Al z O 2 and Al-Doped LiNi x Mn y Co z O 2 via 27 Al MAS NMR Spectroscopy journal June 2016
Nickel-Rich Layered Cathode Materials for Automotive Lithium-Ion Batteries: Achievements and Perspectives journal December 2016
Role of Alumina Coating on Li−Ni−Co−Mn−O Particles as Positive Electrode Material for Lithium-Ion Batteries journal July 2005
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
Probing the Origin of Enhanced Stability of “AlPO4” Nanoparticle Coated LiCoO2 during Cycling to High Voltages: Combined XRD and XPS Studies journal October 2009
Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries journal October 2004
Determination of the Quadrupole Coupling Constant of the Invisible Aluminum Spins in Zeolite HY with 1H/27Al TRAPDOR NMR journal August 1995
Low-Temperature NMR Studies of the Structure and Dynamics of a Novel Series of Acid−Base Complexes of HF with Collidine Exhibiting Scalar Couplings Across Hydrogen Bonds † journal September 2003
Isotropic High Field NMR Spectra of Li-Ion Battery Materials with Anisotropy >1 MHz journal January 2012
Solid Electrolyte Interphase Growth and Capacity Loss in Silicon Electrodes journal June 2016
Cobalt(III) Effect on 27 Al NMR Chemical Shifts in LiAl x Co 1 - x O 2 journal August 2001
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Surface reconstruction and chemical evolution of stoichiometric layered cathode materials for lithium-ion batteries journal March 2014
Metal segregation in hierarchically structured cathode materials for high-energy lithium batteries journal January 2016
High-energy cathode material for long-life and safe lithium batteries journal March 2009
Evolution of redox couples in Li- and Mn-rich cathode materials and mitigation of voltage fade by reducing oxygen release journal July 2018
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Role of surface coating on cathode materials for lithium-ion batteries journal January 2010
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Oxygen Release and Its Effect on the Cycling Stability of LiNi x Mn y Co z O 2 (NMC) Cathode Materials for Li-Ion Batteries journal January 2017
Surface Structure and High-Voltage Charge/Discharge Characteristics of Al-Oxide Coated LiNi 1/3 Co 1/3 Mn 1/3 O 2 Cathodes journal January 2015
Effect of Residual Lithium Compounds on Layer Ni-Rich Li[Ni 0.7 Mn 0.3 ]O 2 journal January 2014
Editors' Choice—Growth of Ambient Induced Surface Impurity Species on Layered Positive Electrode Materials and Impact on Electrochemical Performance journal January 2017
A Study of Li-Ion Cells Operated to 4.5 V and at 55°C journal January 2016

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