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Title: Modification of Ni-Rich FCG NMC and NCA Cathodes by Atomic Layer Deposition: Preventing Surface Phase Transitions for High-Voltage Lithium-Ion Batteries

Journal Article · · Scientific Reports
DOI:https://doi.org/10.1038/srep26532· OSTI ID:1259416
 [1];  [2];  [3];  [1];  [1];  [4];  [4];  [5];  [6];  [6];  [7]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Energy Power Systems, LLC, Pontiac, MI (United States)
  3. PneumatiCoat Technologies, LLC, Broomfield, CO (United States)
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
  5. Energy Power Systems, LLC, Pontiac, MI (United States); XALT Energy, LLC, Midland, MI (United States)
  6. XALT Energy, LLC, Midland, MI (United States)
  7. Univ. of Michigan, Ann Arbor, MI (United States). Dept. of Materials Science and Engineering
+ Show Author Affiliations

The energy density of current lithium-ion batteries (LIBs) based on layered LiMO2 cathodes (M=Ni, Mn, Co: NMC; M=Ni, Co, Al: NCA) needs to be improved significantly in order to compete with internal combustion engines and allow for widespread implementation of electric vehicles (EVs). In this report, we show that atomic layer deposition (ALD) of titania (TiO2) and alumina (Al2O3) on Ni-rich FCG NMC and NCA active material particles could substantially improve LIB performance and allow for increased upper cutoff voltage (UCV) during charging, which delivers significantly increased specific energy utilization. Our results show that Al2O3 coating improved the NMC cycling performance by 40% and the NCA cycling performance by 34% at 1C/₋1C with respectively 4.35V and 4.4V UCV in 2Ah pouch cells. High resolution TEM/SAED structural characterization revealed that Al2O3 coatings prevented surface-initiated layered-to-spinel phase transitions in coated materials which were prevalent in uncoated materials. Lastly, EIS confirmed that Al2O3-coated materials had significantly lower increase in the charge transfer component of impedance during cycling. In conclusion, the ability to mitigate degradation mechanisms for Ni-rich NMC and NCA illustrated in this report provides insight into a method to enable the performance of high-voltage LIBs.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC05-00OR22725; EE0005384; NFE-11-03678; TSA 14-587; LS-111201AMMW; SC0010230
OSTI ID:
1259416
Journal Information:
Scientific Reports, Vol. 6; ISSN 2045-2322
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 167 works
Citation information provided by
Web of Science

References (38)

The energy-storage frontier: Lithium-ion batteries and beyond journal November 2015
Review of the U.S. Department of Energy’s “Deep Dive” Effort to Understand Voltage Fade in Li- and Mn-Rich Cathodes journal October 2015
Recent progress in cathode materials research for advanced lithium ion batteries journal May 2012
Electrodes with High Power and High Capacity for Rechargeable Lithium Batteries journal February 2006
Short-lived charge-transfer excitons in organic photovoltaic cells studied by high-field magneto-photocurrent journal July 2014
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
Understanding the structure and structural degradation mechanisms in high-voltage, lithium-manganese–rich lithium-ion battery cathode oxides: A review of materials diagnostics journal January 2015
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
Electrode Side Reactions, Capacity Loss and Mechanical Degradation in Lithium-Ion Batteries journal January 2015
Aging Analysis of Graphite/LiNi 1/3 Mn 1/3 Co 1/3 O 2 Cells Using XRD, PGAA, and AC Impedance journal January 2015
Narrow Range Cycling and Storage of Commercial Li Ion Cells journal December 2012
Layered-to-Spinel Phase Transition in Li[sub x]MnO[sub 2] journal January 2001
High rate capability caused by surface cubic spinels in Li-rich layer-structured cathodes for Li-ion batteries journal October 2013
The Li-Ion Rechargeable Battery: A Perspective journal January 2013
Unraveling the Voltage-Fade Mechanism in High-Energy-Density Lithium-Ion Batteries: Origin of the Tetrahedral Cations for Spinel Conversion journal October 2014
Demonstrating Oxygen Loss and Associated Structural Reorganization in the Lithium Battery Cathode Li[Ni0.2Li0.2Mn0.6]O2 journal June 2006
Combined Neutron Diffraction, NMR, and Electrochemical Investigation of the Layered-to-Spinel Transformation in LiMnO 2 journal August 2004
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
Unexpected high power performance of atomic layer deposition coated Li[Ni1/3Mn1/3Co1/3]O2 cathodes journal May 2014
Nanostructured high-energy cathode materials for advanced lithium batteries journal October 2012
High-energy cathode material for long-life and safe lithium batteries journal March 2009
A Novel Cathode Material with a Concentration-Gradient for High-Energy and Safe Lithium-Ion Batteries journal February 2010
Mitigating Voltage Fade in Cathode Materials by Improving the Atomic Level Uniformity of Elemental Distribution journal April 2014
A New Type of Protective Surface Layer for High-Capacity Ni-Based Cathode Materials: Nanoscaled Surface Pillaring Layer journal February 2013
Formation of the Spinel Phase in the Layered Composite Cathode Used in Li-Ion Batteries journal December 2012
Tailoring the surface properties of LiNi 0.4 Mn 0.4 Co 0.2 O 2 by titanium substitution for improved high voltage cycling performance journal January 2015
Electrochemical effects of ALD surface modification on combustion synthesized LiNi1/3Mn1/3Co1/3O2 as a layered-cathode material journal March 2011
Effect of Al 2 O 3 Coating on Stabilizing LiNi 0.4 Mn 0.4 Co 0.2 O 2 Cathodes journal August 2015
Unexpected Improved Performance of ALD Coated LiCoO 2 /Graphite Li-Ion Batteries journal September 2012
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
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
Long Range and Short Range Magnetic Order in Orthorhombic LiMnO2 journal February 1997
Crystallographic and magnetic structure of Li2MnO3 journal July 1988
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
Transmission Electron Microscope Studies of LiNi[sub 1/3]Mn[sub 1/3]Co[sub 1/3]O[sub 2] before and after Long-Term Aging at 70°C journal January 2008
Sodium Ion Diffusion in Al 2 O 3 : A Distinct Perspective Compared with Lithium Ion Diffusion journal October 2014
Electrodes with High Power and High Capacity for Rechargeable Lithium Batteries. journal May 2006
Electrode Side Reactions, Capacity Loss and Mechanical Degradation in Lithium Ion Batteries journal April 2015

Cited By (36)

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
A Critical Review: The Impact of the Battery Electrode Material Substrate on the Composition and Properties of Atomic Layer Deposition (ALD) Coatings journal October 2019
Prospect and Reality of Ni-Rich Cathode for Commercialization journal November 2017
MnPO 4 -Coated Li(Ni 0.4 Co 0.2 Mn 0.4 )O 2 for Lithium(-Ion) Batteries with Outstanding Cycling Stability and Enhanced Lithiation Kinetics journal August 2018
Commercialization of Lithium Battery Technologies for Electric Vehicles journal June 2019
On the Functionality of Coatings for Cathode Active Materials in Thiophosphate‐Based All‐Solid‐State Batteries journal May 2019
Sulfolane‐Based Ethylene Carbonate‐Free Electrolytes for LiNi 0.6 Mn 0.2 Co 0.2 O 2 −Li 4 Ti 5 O 12 Batteries journal November 2019
Investigation of Dimethyl Carbonate and Propylene Carbonate Mixtures for LiNi 0.6 Mn 0.2 Co 0.2 O 2 ‐Li 4 Ti 5 O 12 Cells journal July 2019
High‐Voltage Performance of Ni‐Rich NCA Cathodes: Linking Operating Voltage with Cathode Degradation journal August 2019
Simultaneous Stabilization of LiNi 0.76 Mn 0.14 Co 0.10 O 2 Cathode and Lithium Metal Anode by Lithium Bis(oxalato)borate as Additive journal June 2018
Enhanced Electrochemical Performance of LiNi 0.6 Co 0.2 Mn 0.2 O 2 by Expanded Graphite journal August 2019
LiNi0.8Co0.15Al0.05O2 coated by chromium oxide as a cathode material for lithium-ion batteries journal July 2019
Toward Low-Cost, High-Energy Density, and High-Power Density Lithium-Ion Batteries journal June 2017
Degradation Mechanisms and Mitigation Strategies of Nickel-Rich NMC-Based Lithium-Ion Batteries journal October 2019
Building ultraconformal protective layers on both secondary and primary particles of layered lithium transition metal oxide cathodes journal May 2019
Effect of Low-Temperature Al2O3 ALD Coating on Ni-Rich Layered Oxide Composite Cathode on the Long-Term Cycling Performance of Lithium-Ion Batteries journal March 2019
Intrinsic Origins of Crack Generation in Ni-rich LiNi0.8Co0.1Mn0.1O2 Layered Oxide Cathode Material journal January 2017
A novel gelatin-guided mesoporous bowknot-like Co 3 O 4 anode material for high-performance lithium-ion batteries journal January 2017
Room temperature, liquid-phase Al 2 O 3 surface coating approach for Ni-rich layered oxide cathode material journal January 2019
Toward high-performance Li(Ni x Co y Mn z )O 2 cathodes: facile fabrication of an artificial polymeric interphase using functional polyacrylates journal January 2018
Structure- and porosity-tunable, thermally reactive metal organic frameworks for high-performance Ni-rich layered oxide cathode materials with multi-scale pores journal January 2019
Titanium dioxide thin films by atomic layer deposition: a review journal August 2017
Minimized Metal Dissolution from High-Energy Nickel Cobalt Manganese Oxide Cathodes with Al 2 O 3 Coating and Its Effects on Electrolyte Decomposition on Graphite Anodes journal January 2019
The Development and Future of Lithium Ion Batteries journal December 2016
Impact of Temperature and Discharge Rate on the Aging of a LiCoO 2 /LiNi 0.8 Co 0.15 Al 0.05 O 2 Lithium-Ion Pouch Cell journal January 2017
Editors' Choice—Capacity Fading Mechanisms of NCM-811 Cathodes in Lithium-Ion Batteries Studied by X-ray Diffraction and Other Diagnostics journal January 2019
Impact of the Synthesis Conditions on the Performance of LiNi x Co y Al z O 2 with High Ni and Low Co Content journal January 2018
Development of Electrolytes for Single Crystal NMC532/Artificial Graphite Cells with Long Lifetime journal January 2018
Synergistic Modification of Magnesium Fluoride/Sodium for Improving the Electrochemical Performances of High-Nickel Ternary (NCM811) Cathode Materials journal January 2019
Review of Modified Nickel-Cobalt Lithium Aluminate Cathode Materials for Lithium-Ion Batteries journal December 2019
Improved cyclability of Nickel-rich layered oxides journal January 2020
SYNTHESIS OF Li-CONDUCTIVE NANOPARTICLES WITH NASICON-TYPE STRUCTURE journal December 2019
Ultrathin Al2O3 Coating on LiNi0.8Co0.1Mn0.1O2 Cathode Material for Enhanced Cycleability at Extended Voltage Ranges journal February 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
Room temperature, liquid-phase Al 2 O 3 surface coating approach for Ni-rich layered oxide cathode material text January 2019
Atomic Layer Deposition of Al–W–Fluoride on LiCoO 2 Cathodes: Comparison of Particle- and Electrode-Level Coatings journal July 2017

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