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Title: Surface degradation of Li1–xNi0.80Co0.15Al0.05O2 cathodes: Correlating charge transfer impedance with surface phase transformations

Journal Article · · Applied Physics Letters
DOI:https://doi.org/10.1063/1.4954800· OSTI ID:1388017
 [1];  [2];  [2];  [1];  [2];  [3];  [3];  [4];  [2];  [2];  [1]
  1. Binghamton Univ., NY (United States)
  2. Rutgers Univ., New Brunswick, NJ (United States)
  3. Science and Technology Facilities Council (STFC), Oxford (United Kingdom). Diamond Light Source, Ltd.
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
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The pronounced capacity fade in Ni-rich layered oxide lithium ion battery cathodes observed when cycling above 4.1V (versus Li/Li+) is associated with a rise in impedance, which is thought to be due to either bulk structural fatigue or surface reactions with the electrolyte (or combination of both). Here, we examine the surface reactions at electrochemically stressed Li1–xNi0.8Co0.15Al0.05O2 binderfree powder electrodes with a combination of electrochemical impedance spectroscopy, spatially resolving electron microscopy, and spatially averaging X-ray spectroscopy techniques. We circumvent issues associated with cycling by holding our electrodes at high states of charge (4.1V, 4.5V, and 4.75V) for extended periods and correlate charge-transfer impedance rises observed at high voltages with surface modifications retained in the discharged state (2.7 V). The surface modifications involve significant cation migration (and disorder) along with Ni and Co reduction, and can occur even in the absence of significant Li2CO3 and LiF. These data provide evidence that surface oxygen loss at the highest levels of Li+ extraction is driving the rise in impedance.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Northeastern Center for Chemical Energy Storage (NECCES)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0001294; AC02-05CH11231; SC0012583
OSTI ID:
1388017
Alternate ID(s):
OSTI ID: 1259367
Journal Information:
Applied Physics Letters, Vol. 108, Issue 26; Related Information: NECCES partners with Stony Brook University (lead); Argonne National Laboratory; Binghamton University; Brookhaven National University; University of California, San Diego; University of Cambridge, UK; Lawrence Berkeley National Laboratory; Massachusetts Institute of Technology; University of Michigan; Rutgers University; ISSN 0003-6951
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 60 works
Citation information provided by
Web of Science

References (22)

Role of Alumina Coating on Li−Ni−Co−Mn−O Particles as Positive Electrode Material for Lithium-Ion Batteries journal July 2005
The cathode–electrolyte interface in the Li-ion battery journal November 2004
Possible Explanation for the Efficiency of Al-Based Coatings on LiCoO 2 : Surface Properties of LiCo 1− x Al x O 2 Solid Solution journal December 2009
Microscopy and Spectroscopy of Lithium Nickel Oxide-Based Particles Used in High Power Lithium-Ion Cells journal January 2003
Lithium Batteries and Cathode Materials journal October 2004
Influence of the PVdF binder on the stability of LiCoO2 electrodes journal December 2005
Cobalt dissolution in LiCoO2-based non-aqueous rechargeable batteries journal January 1996
Surface reconstruction and chemical evolution of stoichiometric layered cathode materials for lithium-ion batteries journal March 2014
Investigation of positive electrodes after cycle testing of high-power Li-ion battery cells II journal December 2007
Microstructure of LiCoO 2 with and without “AlPO 4 ” Nanoparticle Coating:  Combined STEM and XPS Studies journal November 2007
Microstructural Changes in LiNi0.8Co0.15Al0.05O2 Positive Electrode Material during the First Cycle journal January 2011
Surface Characterization of Electrodes from High Power Lithium-Ion Batteries journal January 2002
AC Impedance Analysis of Polycrystalline Insertion Electrodes: Application to Li[sub 1−x]CoO[sub 2] journal January 1985
Degradation mechanisms of lithium-rich nickel manganese cobalt oxide cathode thin films 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
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
Effect of Residual Lithium Compounds on Layer Ni-Rich Li[Ni 0.7 Mn 0.3 ]O 2 journal January 2014
Nickel-Rich and Lithium-Rich Layered Oxide Cathodes: Progress and Perspectives journal October 2015
Electrode–Electrolyte Interface in Li-Ion Batteries: Current Understanding and New Insights journal October 2015
X-Ray Spectroscopy of Ultra-Thin Oxide/Oxide Heteroepitaxial Films: A Case Study of Single-Nanometer VO2/TiO2 journal August 2015
Study of the Failure Mechanisms of LiNi 0.8 Mn 0.1 Co 0.1 O 2 Cathode Material for Lithium Ion Batteries journal January 2015
Degradation Mechanism of LiNi 0.82 Co 0.15 Al 0.03 O 2 Positive Electrodes of a Lithium-Ion Battery by a Long-Term Cycling Test journal January 2014

Cited By (6)

A Comprehensive Analysis of the Interphasial and Structural Evolution over Long‐Term Cycling of Ultrahigh‐Nickel Cathodes in Lithium‐Ion Batteries journal October 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
Synchrotron-Based X-ray Absorption Fine Structures, X-ray Diffraction, and X-ray Microscopy Techniques Applied in the Study of Lithium Secondary Batteries journal April 2018
Synthesis and Characterization of Core-Shell Nanocrystals of Co-Rich Cathodes journal October 2019
Editors' Choice—Capacity Fading Mechanisms of NCM-811 Cathodes in Lithium-Ion Batteries Studied by X-ray Diffraction and Other Diagnostics journal January 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

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Related Subjects

25 ENERGY STORAGE
42 ENGINEERING
36 MATERIALS SCIENCE
75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY
energy storage (including batteries and capacitors)
defects
charge transport
materials and chemistry by design
synthesis (novel materials)