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Title: Beneficial Effects of La 0.5 Sr 0.5 CoO 3 Coatings on Thin‐Film LiMn 2 O 4 Cathodes for Lithium Ion Batteries

Journal Article · · Advanced Sustainable Systems
 [1];  [1];  [2];  [2];  [2]; ORCiD logo [1]
  1. Department of Materials Science and Engineering Northwestern University Evanston IL 60208 USA
  2. NUANCE Center Northwestern University Evanston IL 60208 USA

Abstract The severe capacity loss of spinel LiMn 2 O 4 (LMO) limits the utility of this otherwise promising lithium ion battery cathode material. One of the strategies to mitigate capacity fade is applying a coating on LMO particle surfaces. While this approach yields promising results, there is limited understanding of mechanisms whereby coatings improve LMO capacity retention. Herein, the effects of a new protective coating material, La 0.5 Sr 0.5 CoO 3 (LSCO), in a thin‐film battery geometry that is amenable to fundamental studies of electrode processes, are reported. RF sputtering deposition is used to produce high quality 25–100 nm LMO cathodes on Al 2 O 3 substrates with an intervening Pt/Ti back‐side contact layer. Cycling of the un‐coated cathodes results in capacity loss of 18% over 300 cycles. Adding a 2 nm LSCO layer reduces the capacity loss to 3%. While this may be due in part to reduced Mn dissolution, scanning transmission electron microscopy results indicate that the coating helps to preserve crystallinity and reduce lattice structure distortion due to inhibited formation of defect tetragonal spinel. Three‐electrode electrochemical impedance spectroscopy results reveal that the LSCO coating increases charge transfer and ohmic resistances, but the increases are generally too small to significantly impact cell performance even at high C‐rates.

Sponsoring Organization:
USDOE
OSTI ID:
1973540
Alternate ID(s):
OSTI ID: 1983441
Journal Information:
Advanced Sustainable Systems, Journal Name: Advanced Sustainable Systems Vol. 7 Journal Issue: 9; ISSN 2366-7486
Publisher:
Wiley Blackwell (John Wiley & Sons)Copyright Statement
Country of Publication:
Germany
Language:
English

References (57)

Surface modification of LiMn2O4 cathode with LaCoO3 by a molten salt method for lithium ion batteries journal March 2021
Improved Electrochemical Performances of Surface-Modified Spinel LiMn[sub 2]O[sub 4] for Long Cycle Life Lithium-Ion Batteries journal January 2003
Improved capacity retention in rechargeable 4 V lithium/lithium-manganese oxide (spinel) cells journal April 1994
Capacity Fading on Cycling of 4 V Li∕LiMn[sub 2]O[sub 4] Cells journal January 1997
Dissolution of Spinel Oxides and Capacity Losses in 4V Li / LixMn2O4 Cells journal January 1996
Capacity fading of LixMn2O4 spinel electrodes studied by XRD and electroanalytical techniques journal September 1999
Issues and challenges facing rechargeable lithium batteries journal November 2001
Study on Li+-ion diffusion in nano-crystalline LiMn2O4 thin film cathode grown by pulsed laser deposition using CV, EIS and PITT techniques journal September 2008
High Rate, Superior Capacity Retention LiMn[sub 2−2y]Li[sub y]Ni[sub y]O[sub 4] Spinel Cathodes for Lithium-Ion Batteries journal January 2003
Revealing the complex layered-mosaic structure of the cathode electrolyte interphase in Li-ion batteries journal September 2020
A Physically-Based Equivalent Circuit Model for the Impedance of a LiFePO 4 /Graphite 26650 Cylindrical Cell journal January 2017
The Impedance Response of a Porous Electrode Composed of Intercalation Particles journal January 2000
Electrode–Electrolyte Interface in Li-Ion Batteries: Current Understanding and New Insights journal October 2015
Elevated temperature cycling stability and electrochemical impedance of LiMn2O4 cathodes with nanoporous ZrO2 and TiO2 coatings journal August 2010
Impedance Spectroscopy book January 2005
Materials Challenges and Opportunities of Lithium Ion Batteries journal January 2011
Surface Structure Evolution of LiMn 2 O 4 Cathode Material upon Charge/Discharge journal May 2014
Effects of Nanoparticle Geometry and Size Distribution on Diffusion Impedance of Battery Electrodes journal November 2012
Enhancing the electrochemical performance of LiNi0.5Mn1.5O4 cathode material by a conductive LaCoO3 coating journal June 2021
Disproportionation of stoichiometric LiMn2O4 on annealing in oxygen journal January 2004
Trap State Spectroscopy of LiMyMn2-yO4 (M = Mn, Ni, Co): Guiding Principles for Electrochemical Performance journal February 2013
Oxygen loss and surface degradation during electrochemical cycling of lithium-ion battery cathode material LiMn 2 O 4 journal January 2019
A Truncated Manganese Spinel Cathode for Excellent Power and Lifetime in Lithium-Ion Batteries journal February 2012
Enhanced electrocatalytic activity of three-dimensionally-ordered macroporous La 0.6 Sr 0.4 CoO 3−δ perovskite oxide for Li–O 2 battery application journal January 2016
Pulsed Laser Deposition and Characterization of Heteroepitaxial LiMn 2 O 4 /La 0.5 Sr 0.5 CoO 3 Bilayer Thin Films as Model Lithium Ion Battery Cathodes journal January 2018
In Situ Synchrotron X-Ray Diffraction Studies of the Phase Transitions in Li[sub x]Mn[sub 2]O[sub 4] Cathode Materials journal January 1999
The Li-Ion Rechargeable Battery: A Perspective journal January 2013
Ethyl 3,3,3-trifluoropropanoate as an additive to improve the cycling performance of LiMn 2 O 4 cathode on lithium-ion batteries at elevated temperature journal June 2016
Fast Li-Ion Insertion into Nanosized LiMn 2 O 4 without Domain Boundaries journal January 2010
Effectively suppressing dissolution of manganese from spinel lithium manganate via a nanoscale surface-doping approach journal December 2014
Degradation mechanisms in doped spinels of LiM0.05Mn1.95O4 (M=Li, B, Al, Co, and Ni) for Li secondary batteries journal July 2000
Onset Mechanism of Jahn-Teller Distortion in 4 V LiMn[sub 2]O[sub 4] and Its Suppression by LiM[sub 0.05]Mn[sub 1.95]O[sub 4] (M = Co, Ni) Coating journal January 2005
Factors Affecting the Stabilization of Mn Spinel Capacity upon Staring and Cycling at High Temperatures journal August 1998
Separation of Charge Transfer and Contact Resistance in LiFePO 4 -Cathodes by Impedance Modeling journal January 2012
Frequency response of unified dielectric and conductive systems involving an exponential distribution of activation energies journal September 1985
Recent developments in cathode materials for lithium ion batteries journal February 2010
Simulation of the surface structure of lithium manganese oxide spinel journal May 2011
Lithium insertion into manganese spinels journal April 1983
Unusual Spinel-to-Layered Transformation in LiMn 2 O 4 Cathode Explained by Electrochemical and Thermal Stability Investigation journal September 2017
Review—Manganese Dissolution from Spinel Cathode: Few Unanswered Questions journal December 2016
Nanosize Effect on High-Rate Li-Ion Intercalation in LiCoO 2 Electrode journal June 2007
Solid-state chemistry of lithium power sources† journal January 1997
Atomic-Scale Tracking of a Phase Transition from Spinel to Rocksalt in Lithium Manganese Oxide journal January 2017
Lithium batteries: Status, prospects and future journal May 2010
Li-ion transport kinetics in LiMn2O4 thin films prepared by radio frequency magnetron sputtering journal May 2008
Solid-Solution Li Intercalation as a Function of Cation Order/Disorder in the High-Voltage Li x Ni 0.5 Mn 1.5 O 4 Spinel journal July 2013
The Importance of Interphase Contacts in Li Ion Electrodes: The Meaning of the High-Frequency Impedance Arc journal January 2008
Surface Mn Oxidation State Controlled Spinel LiMn 2 O 4 as a Cathode Material for High-Energy Li-Ion Batteries journal May 2015
High-throughput computational design of cathode coatings for Li-ion batteries journal December 2016
A Guide to Li-Ion Coin-Cell Electrode Making for Academic Researchers journal January 2011
Suppressing Manganese Dissolution from Lithium Manganese Oxide Spinel Cathodes with Single-Layer Graphene journal June 2015
Enhanced cycle stability at high rate and excellent high rate capability of La0.7Sr0.3Mn0.7Co0.3O3-coated LiMn2O4 journal January 2015
Surface coating of spinel LiMn2O4 cathode electrode with lithium–nickel–manganese-oxide by RF sputtering method for lithium-ion batteries journal September 2014
Study on Electrode Kinetics of Li + Insertion in Li x Mn 2 O 4 (0 ≤ x ≤ 1) by Electrochemical Impedance Spectroscopy journal July 2007
Electrochemistry of Manganese Dioxide in Lithium Nonaqueous Cell journal January 1990
Ultrathin Lithium-Ion Conducting Coatings for Increased Interfacial Stability in High Voltage Lithium-Ion Batteries journal May 2014
Surface structure and equilibrium particle shape of the LiMn 2 O 4 spinel from first-principles calculations journal February 2013

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