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Title: Descriptor-Based Analysis of Atomic Layer Deposition Mechanisms on Spinel LiMn2O4 Lithium-Ion Battery Cathodes

Abstract

Protective coatings have been shown to effectively suppress Mn ion dissolution from the spinel LiMn2O4 lithium-ion battery cathode by stabilizing the surface against undesired side reactions with the electrolyte. In spite of extensive study, however, there remains a lack of atomic-scale understanding of how such coatings are deposited, and no molecular-level descriptor to predict trends in deposition mechanisms has been identified. We have recently shown that Al2O3 coatings grown by atomic layer deposition (ALD) with alternating trimethylaluminum (TMA) and water exposures exhibit submonolayer growth because of precursor decomposition on the lithium manganate spinel (LMO) surface during early ALD pulses. In the present work, we elucidate the underlying mechanisms of this Al2O3 ALD process using density functional theory (DFT) calculations and X-ray photoelectron spectroscopy (XPS) experiments, and we introduce a generalized descriptor-based framework to understand the resulting trends across a spectrum of surface structures and functionalities. We demonstrate that all decomposition products, including CH3 -aluminum adducts and dissociated CH3 groups, are Lewis bases and are coordinated to oxygen atoms on the LMO surface, leading to charge transfer to Lewis acidic Mn 3d states. Inert-transfer XPS supports these theoretical predictions, showing an increase in near-surface Mn3+ content following TMA exposure and shiftsmore » in C is spectra consistent with C-O bond formation. We extend the DFT studies to various low- and high-index LMO surface facets, as a proxy for tuning the Lewis acid-base interactions between surface-bound CH3* and near-surface Mn ions. The thermochemistry for TMA reactions on these chemically distinct LMO surfaces demonstrates that ALD is structure-sensitive and that there is higher reactivity for TMA decomposition and Al2O3 nucleation near LMO steps and defects. Motivated by the Lewis basic character of the decomposition products, we introduce the oxygen vacancy formation energy as a descriptor for decomposition energetics, and we demonstrate that all energetics are correlated to this quantity through the number of electrons that are transferred along the reaction coordinate. Finally, based on these findings, we hypothesize that improved electrochemical cycling with only 1-2 ALD cycles may be due to selective passivation of defect sites on the LMO surface that are more susceptible to Mn dissolution, and we suggest that similar descriptor-based analyses could be useful for the study of other ALD coatings on oxide substrates.« less

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [1]
  1. Purdue Univ., West Lafayette, IN (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States); Univ. of Missouri, Columbia, MO (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Electrical Energy Storage (CEES); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1765469
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 32; Journal Issue: 5; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; adsorption; organic reactions; ions; atomic layer deposition; transition metals

Citation Formats

Warburton, Robert E., Young, Matthias J., Letourneau, Steven, Elam, Jeffrey W., and Greeley, Jeffrey. Descriptor-Based Analysis of Atomic Layer Deposition Mechanisms on Spinel LiMn2O4 Lithium-Ion Battery Cathodes. United States: N. p., 2020. Web. https://doi.org/10.1021/acs.chemmater.9b03809.
Warburton, Robert E., Young, Matthias J., Letourneau, Steven, Elam, Jeffrey W., & Greeley, Jeffrey. Descriptor-Based Analysis of Atomic Layer Deposition Mechanisms on Spinel LiMn2O4 Lithium-Ion Battery Cathodes. United States. https://doi.org/10.1021/acs.chemmater.9b03809
Warburton, Robert E., Young, Matthias J., Letourneau, Steven, Elam, Jeffrey W., and Greeley, Jeffrey. Tue . "Descriptor-Based Analysis of Atomic Layer Deposition Mechanisms on Spinel LiMn2O4 Lithium-Ion Battery Cathodes". United States. https://doi.org/10.1021/acs.chemmater.9b03809. https://www.osti.gov/servlets/purl/1765469.
@article{osti_1765469,
title = {Descriptor-Based Analysis of Atomic Layer Deposition Mechanisms on Spinel LiMn2O4 Lithium-Ion Battery Cathodes},
author = {Warburton, Robert E. and Young, Matthias J. and Letourneau, Steven and Elam, Jeffrey W. and Greeley, Jeffrey},
abstractNote = {Protective coatings have been shown to effectively suppress Mn ion dissolution from the spinel LiMn2O4 lithium-ion battery cathode by stabilizing the surface against undesired side reactions with the electrolyte. In spite of extensive study, however, there remains a lack of atomic-scale understanding of how such coatings are deposited, and no molecular-level descriptor to predict trends in deposition mechanisms has been identified. We have recently shown that Al2O3 coatings grown by atomic layer deposition (ALD) with alternating trimethylaluminum (TMA) and water exposures exhibit submonolayer growth because of precursor decomposition on the lithium manganate spinel (LMO) surface during early ALD pulses. In the present work, we elucidate the underlying mechanisms of this Al2O3 ALD process using density functional theory (DFT) calculations and X-ray photoelectron spectroscopy (XPS) experiments, and we introduce a generalized descriptor-based framework to understand the resulting trends across a spectrum of surface structures and functionalities. We demonstrate that all decomposition products, including CH3 -aluminum adducts and dissociated CH3 groups, are Lewis bases and are coordinated to oxygen atoms on the LMO surface, leading to charge transfer to Lewis acidic Mn 3d states. Inert-transfer XPS supports these theoretical predictions, showing an increase in near-surface Mn3+ content following TMA exposure and shifts in C is spectra consistent with C-O bond formation. We extend the DFT studies to various low- and high-index LMO surface facets, as a proxy for tuning the Lewis acid-base interactions between surface-bound CH3* and near-surface Mn ions. The thermochemistry for TMA reactions on these chemically distinct LMO surfaces demonstrates that ALD is structure-sensitive and that there is higher reactivity for TMA decomposition and Al2O3 nucleation near LMO steps and defects. Motivated by the Lewis basic character of the decomposition products, we introduce the oxygen vacancy formation energy as a descriptor for decomposition energetics, and we demonstrate that all energetics are correlated to this quantity through the number of electrons that are transferred along the reaction coordinate. Finally, based on these findings, we hypothesize that improved electrochemical cycling with only 1-2 ALD cycles may be due to selective passivation of defect sites on the LMO surface that are more susceptible to Mn dissolution, and we suggest that similar descriptor-based analyses could be useful for the study of other ALD coatings on oxide substrates.},
doi = {10.1021/acs.chemmater.9b03809},
journal = {Chemistry of Materials},
number = 5,
volume = 32,
place = {United States},
year = {2020},
month = {2}
}

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Works referenced in this record:

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Improved capacity retention in rechargeable 4 V lithium/lithium-manganese oxide (spinel) cells
journal, April 1994


Reaction Energy for LiMn[sub 2]O[sub 4] Spinel Dissolution in Acid
journal, January 2006

  • Benedek, R.; Thackeray, M. M.
  • Electrochemical and Solid-State Letters, Vol. 9, Issue 6
  • DOI: 10.1149/1.2188071

First-Principles Predictions and in Situ Experimental Validation of Alumina Atomic Layer Deposition on Metal Surfaces
journal, November 2014

  • Lu, Junling; Liu, Bin; Guisinger, Nathan P.
  • Chemistry of Materials, Vol. 26, Issue 23
  • DOI: 10.1021/cm503178j

Projector augmented-wave method
journal, December 1994


On the Oxidation State of Manganese Ions in Li-Ion Battery Electrolyte Solutions
journal, January 2017

  • Banerjee, Anjan; Shilina, Yuliya; Ziv, Baruch
  • Journal of the American Chemical Society, Vol. 139, Issue 5
  • DOI: 10.1021/jacs.6b10781

LiMn 2 O 4 @Au Particles as Cathodes for Li-Ion Batteries
journal, November 2014

  • Esbenshade, Jennifer L.; Fox, Mathew D.; Gewirth, Andrew A.
  • Journal of The Electrochemical Society, Vol. 162, Issue 1
  • DOI: 10.1149/2.0241501jes

Thermodynamic Stability of Low- and High-Index Spinel LiMn 2 O 4 Surface Terminations
journal, April 2016

  • Warburton, Robert E.; Iddir, Hakim; Curtiss, Larry A.
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 17
  • DOI: 10.1021/acsami.6b01069

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Synthesis, Characterization, and Structural Modeling of High-Capacity, Dual Functioning MnO 2 Electrode/Electrocatalysts for Li-O 2 Cells
journal, July 2012

  • Trahey, Lynn; Karan, Naba K.; Chan, Maria K. Y.
  • Advanced Energy Materials, Vol. 3, Issue 1
  • DOI: 10.1002/aenm.201200037

Are Spin-Forbidden Crossings a Bottleneck in Methanol Oxidation?
journal, October 2009

  • Goodrow, Anthony; Bell, Alexis T.; Head-Gordon, Martin
  • The Journal of Physical Chemistry C, Vol. 113, Issue 45
  • DOI: 10.1021/jp906603r

Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study
journal, January 1998

  • Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y.
  • Physical Review B, Vol. 57, Issue 3, p. 1505-1509
  • DOI: 10.1103/PhysRevB.57.1505

Electrochemical Stiffness Changes in Lithium Manganese Oxide Electrodes
journal, December 2016

  • Çapraz, Ömer Özgür; Bassett, Kimberly L.; Gewirth, Andrew A.
  • Advanced Energy Materials, Vol. 7, Issue 7
  • DOI: 10.1002/aenm.201601778

Density-functional theory and strong interactions: Orbital ordering in Mott-Hubbard insulators
journal, August 1995


Thermodynamic Aspects of Cathode Coatings for Lithium-Ion Batteries
journal, August 2014

  • Aykol, Muratahan; Kirklin, Scott; Wolverton, C.
  • Advanced Energy Materials, Vol. 4, Issue 17
  • DOI: 10.1002/aenm.201400690

Comprehensive Enhancement of Nanostructured Lithium-Ion Battery Cathode Materials via Conformal Graphene Dispersion
journal, March 2017


Atomic Layer Deposited MgO: A Lower Overpotential Coating for Li[Ni 0.5 Mn 0.3 Co 0.2 ]O 2 Cathode
journal, March 2017

  • Laskar, Masihhur R.; Jackson, David H. K.; Xu, Shenzhen
  • ACS Applied Materials & Interfaces, Vol. 9, Issue 12
  • DOI: 10.1021/acsami.6b16562

Ab initiomolecular dynamics for liquid metals
journal, January 1993


Density-functional theory and NiO photoemission spectra
journal, December 1993


A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000

  • Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes
  • The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904
  • DOI: 10.1063/1.1329672

Structure and electrochemical characterization of Li1+xMn2−xO4 spinels for rechargeable lithium batteries
journal, September 1999


Surface modifications of Li-ion battery electrodes with various ultrathin amphoteric oxide coatings for enhanced cycleability
journal, December 2012


Acid–Base Interaction and Its Role in Alkane Dissociative Chemisorption on Oxide Surfaces
journal, November 2014

  • Chrétien, Steeve; Metiu, Horia
  • The Journal of Physical Chemistry C, Vol. 118, Issue 47
  • DOI: 10.1021/jp507207b

Effectively suppressing dissolution of manganese from spinel lithium manganate via a nanoscale surface-doping approach
journal, December 2014

  • Lu, Jun; Zhan, Chun; Wu, Tianpin
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms6693

Dissociation and oxidation of methanol on Cu()
journal, June 2002


Improving the high-temperature performance of LiMn2O4 spinel electrodes by coating the active mass with MgO via a sonochemical method
journal, November 2003


Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


Manganese oxides for lithium batteries
journal, January 1997


Structural Fatigue in Spinel Electrodes in High Voltage (4 V) Li/Li[sub x]Mn[sub 2]O[sub 4] Cells
journal, January 1999

  • Thackeray, Michael M.
  • Electrochemical and Solid-State Letters, Vol. 1, Issue 1
  • DOI: 10.1149/1.1390617

Optimizing AlF 3 atomic layer deposition using trimethylaluminum and TaF 5 : Application to high voltage Li-ion battery cathodes
journal, May 2016

  • Jackson, David H. K.; Laskar, Masihhur R.; Fang, Shuyu
  • Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 34, Issue 3
  • DOI: 10.1116/1.4943385

Structural Changes of LiMn[sub 2]O[sub 4] Spinel Electrodes during Electrochemical Cycling
journal, January 1999

  • Choa, Jaephil
  • Journal of The Electrochemical Society, Vol. 146, Issue 10
  • DOI: 10.1149/1.1392517

The Electrochemical Stability of Spinel Electrodes Coated with ZrO2, Al2O3, and SiO2 from Colloidal Suspensions
journal, January 2004

  • Kim, J.-S.; Johnson, C. S.; Vaughey, J. T.
  • Journal of The Electrochemical Society, Vol. 151, Issue 10, p. A1755-A1761
  • DOI: 10.1149/1.1793713

Surface Chemistry of Trimethylaluminum on Pd(111) and Pt(111)
journal, August 2015

  • Gharachorlou, Amir; Detwiler, Michael D.; Mayr, Lukas
  • The Journal of Physical Chemistry C, Vol. 119, Issue 33
  • DOI: 10.1021/jp512915f

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


DFT+U Investigation of Propene Oxidation over Bismuth Molybdate: Active Sites, Reaction Intermediates, and the Role of Bismuth
journal, March 2013

  • Getsoian, Andrew “Bean”; Shapovalov, Vladimir; Bell, Alexis T.
  • The Journal of Physical Chemistry C, Vol. 117, Issue 14
  • DOI: 10.1021/jp400440p

Lithium insertion into manganese spinels
journal, April 1983

  • Thackeray, M. M.; David, W. I. F.; Bruce, P. G.
  • Materials Research Bulletin, Vol. 18, Issue 4, p. 461-472
  • DOI: 10.1016/0025-5408(83)90138-1

Band theory and Mott insulators: Hubbard U instead of Stoner I
journal, July 1991

  • Anisimov, Vladimir I.; Zaanen, Jan; Andersen, Ole K.
  • Physical Review B, Vol. 44, Issue 3, p. 943-954
  • DOI: 10.1103/PhysRevB.44.943

Surface phase diagram and stability of (001) and (111) LiM n 2 O 4 spinel oxides
journal, September 2015


ALD for clean energy conversion, utilization, and storage
journal, November 2011

  • Elam, Jeffrey W.; Dasgupta, Neil P.; Prinz, Fritz B.
  • MRS Bulletin, Vol. 36, Issue 11, p. 899-906
  • DOI: 10.1557/mrs.2011.265

Towards First Principles-Based Prediction of Highly Accurate Electrochemical Pourbaix Diagrams
journal, July 2015

  • Zeng, Zhenhua; Chan, Maria K. Y.; Zhao, Zhi-Jian
  • The Journal of Physical Chemistry C, Vol. 119, Issue 32
  • DOI: 10.1021/acs.jpcc.5b03169

High-throughput computational design of cathode coatings for Li-ion batteries
journal, December 2016

  • Aykol, Muratahan; Kim, Soo; Hegde, Vinay I.
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms13779

Preparation of a new crystal form of manganese dioxide: λ-MnO2
journal, September 1981


The Unified Electrochemical Band Diagram Framework: Understanding the Driving Forces of Materials Electrochemistry
journal, August 2018

  • Young, Matthias J.; Holder, Aaron M.; Musgrave, Charles B.
  • Advanced Functional Materials, Vol. 28, Issue 41
  • DOI: 10.1002/adfm.201803439

Inorganic electrolyte additives to suppress the degradation of graphite anodes by dissolved Mn(II) for lithium-ion batteries
journal, June 2003


Suppressing Manganese Dissolution from Lithium Manganese Oxide Spinel Cathodes with Single-Layer Graphene
journal, June 2015

  • Jaber-Ansari, Laila; Puntambekar, Kanan P.; Kim, Soo
  • Advanced Energy Materials, Vol. 5, Issue 17
  • DOI: 10.1002/aenm.201500646

Mechanisms for the Trimethylaluminum Reaction in Aluminum Oxide Atomic Layer Deposition on Sulfur Passivated Germanium
journal, August 2011

  • Delabie, Annelies; Sioncke, Sonja; Rip, Jens
  • The Journal of Physical Chemistry C, Vol. 115, Issue 35
  • DOI: 10.1021/jp206070y

Selective metal deposition at graphene line defects by atomic layer deposition
journal, September 2014

  • Kim, Kwanpyo; Lee, Han-Bo-Ram; Johnson, Richard W.
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5781

High energy photoelectron spectroscopy of transition metal complexes. Part 2.—Metallocenes
journal, January 1973

  • Barber, M.; Connor, J. A.; Derrick, L. M. R.
  • J. Chem. Soc., Faraday Trans. 2, Vol. 69, Issue 0
  • DOI: 10.1039/F29736900559

Porous Alumina Protective Coatings on Palladium Nanoparticles by Self-Poisoned Atomic Layer Deposition
journal, May 2012

  • Lu, Junling; Liu, Bin; Greeley, Jeffrey P.
  • Chemistry of Materials, Vol. 24, Issue 11
  • DOI: 10.1021/cm300203s

Role of Disproportionation in the Dissolution of Mn from Lithium Manganate Spinel
journal, September 2017


Degradation of Ethylene Carbonate Electrolytes of Lithium Ion Batteries via Ring Opening Activated by LiCoO 2 Cathode Surfaces and Electrolyte Species
journal, September 2016

  • Tebbe, Jonathon L.; Fuerst, Thomas F.; Musgrave, Charles B.
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 40
  • DOI: 10.1021/acsami.6b06157

Ultrathin Surface Coatings for Improved Electrochemical Performance of Lithium Ion Battery Electrodes at Elevated Temperature
journal, May 2012

  • Zhao, Jianqing; Wang, Ying
  • The Journal of Physical Chemistry C, Vol. 116, Issue 22
  • DOI: 10.1021/jp3010629

Operando Observations and First-Principles Calculations of Reduced Lithium Insertion in Au-Coated LiMn 2 O 4
journal, January 2019

  • Bassett, Kimberly L.; Warburton, Robert E.; Deshpande, Siddharth
  • Advanced Materials Interfaces, Vol. 6, Issue 4
  • DOI: 10.1002/admi.201801923

Density functional theory study of HfCl4, ZrCl4, and Al(CH3)3 decomposition on hydroxylated SiO2: Initial stage of high- k atomic layer deposition
journal, July 2003

  • Jeloaica, L.; Estève, A.; Djafari Rouhani, M.
  • Applied Physics Letters, Vol. 83, Issue 3
  • DOI: 10.1063/1.1587261

Mechanism for Al2O3 Atomic Layer Deposition on LiMn2O4 from In Situ Measurements and Ab Initio Calculations
journal, October 2018


Mn(II) deposition on anodes and its effects on capacity fade in spinel lithium manganate–carbon systems
journal, September 2013

  • Zhan, Chun; Lu, Jun; Jeremy Kropf, A.
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms3437

A study on capacity fading of lithium-ion battery with manganese spinel positive electrode during cycling
journal, April 2006


Importance of Steric Effects in Cluster Models of Silicon Surface Chemistry:  ONIOM Studies of the Atomic Layer Deposition (ALD) of Al 2 O 3 on H/Si(111)
journal, April 2004

  • Halls, Mathew D.; Raghavachari, Krishnan
  • The Journal of Physical Chemistry A, Vol. 108, Issue 15
  • DOI: 10.1021/jp037014m

Degradation mechanism of spinel LiAl0.2Mn1.8O4 cathode materials on high temperature cycling
journal, January 2001

  • Sun, Y. -K.; Yoon, C. S.; Kim, C. K.
  • Journal of Materials Chemistry, Vol. 11, Issue 10
  • DOI: 10.1039/B103709A

Microstructure-Dependent Nucleation in Atomic Layer Deposition of Pt on TiO 2
journal, December 2011

  • Lee, Han-Bo-Ram; Bent, Stacey F.
  • Chemistry of Materials, Vol. 24, Issue 2
  • DOI: 10.1021/cm202764b

Trimethylaluminum and Oxygen Atomic Layer Deposition on Hydroxyl-Free Cu(111)
journal, July 2015

  • Gharachorlou, Amir; Detwiler, Michael D.; Gu, Xiang-Kui
  • ACS Applied Materials & Interfaces, Vol. 7, Issue 30
  • DOI: 10.1021/acsami.5b03598

Relationship between the electrochemical and particle properties of LiMn2O4 prepared by ultrasonic spray pyrolysis
journal, May 2004


Quantum chemical study of the mechanism of aluminum oxide atomic layer deposition
journal, May 2002

  • Widjaja, Yuniarto; Musgrave, Charles B.
  • Applied Physics Letters, Vol. 80, Issue 18
  • DOI: 10.1063/1.1473237

Crystallographic facetting in solid-state reacted LiMn2O4 spinel powder
journal, June 2001


Improved initial guess for minimum energy path calculations
journal, June 2014

  • Smidstrup, Søren; Pedersen, Andreas; Stokbro, Kurt
  • The Journal of Chemical Physics, Vol. 140, Issue 21
  • DOI: 10.1063/1.4878664

Crystal Surface and State of Charge Dependencies of Electrolyte Decomposition on LiMn 2 O 4 Cathode
journal, January 2014

  • Kumar, Nitin; Leung, Kevin; Siegel, Donald J.
  • Journal of The Electrochemical Society, Vol. 161, Issue 8
  • DOI: 10.1149/2.009408jes

Studies of Capacity Losses in Cycles and Storages for a Li[sub 1.1]Mn[sub 1.9]O[sub 4] Positive Electrode
journal, January 2004

  • Saitoh, Motoharu; Sano, Mitsuru; Fujita, Miho
  • Journal of The Electrochemical Society, Vol. 151, Issue 1
  • DOI: 10.1149/1.1630038

A DFT Study of the Al 2 O 3 Atomic Layer Deposition on SAMs:  Effect of SAM Termination
journal, February 2004

  • Xu, Ye; Musgrave, Charles B.
  • Chemistry of Materials, Vol. 16, Issue 4
  • DOI: 10.1021/cm035009p

Thermal Decomposition of LiPF[sub 6]-Based Electrolytes for Lithium-Ion Batteries
journal, January 2005

  • Campion, Christopher L.; Li, Wentao; Lucht, Brett L.
  • Journal of The Electrochemical Society, Vol. 152, Issue 12
  • DOI: 10.1149/1.2083267

Chemistry of Lewis Acid–Base Pairs on Oxide Surfaces
journal, April 2012

  • Metiu, Horia; Chrétien, Steeve; Hu, Zhenpeng
  • The Journal of Physical Chemistry C, Vol. 116, Issue 19
  • DOI: 10.1021/jp301341t

Atomic Layer Deposition of Al 2 O 3 –Ga 2 O 3 Alloy Coatings for Li[Ni 0.5 Mn 0.3 Co 0.2 ]O 2 Cathode to Improve Rate Performance in Li-Ion Battery
journal, April 2016

  • Laskar, Masihhur R.; Jackson, David H. K.; Guan, Yingxin
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 16
  • DOI: 10.1021/acsami.5b11878

Theoretical Study of Atomic Layer Deposition Reaction Mechanism and Kinetics for Aluminum Oxide Formation at Graphene Nanoribbon Open Edges
journal, May 2010

  • Xu, Kun; Ye, Peide D.
  • The Journal of Physical Chemistry C, Vol. 114, Issue 23
  • DOI: 10.1021/jp101387g

Ab Initio Modeling of Electrolyte Molecule Ethylene Carbonate Decomposition Reaction on Li(Ni,Mn,Co)O 2 Cathode Surface
journal, June 2017

  • Xu, Shenzhen; Luo, Guangfu; Jacobs, Ryan
  • ACS Applied Materials & Interfaces, Vol. 9, Issue 24
  • DOI: 10.1021/acsami.7b03435

High-Rate Spinel LiMn 2 O 4 (LMO) Following Carbonate Removal and Formation of Li-Rich Interface by ALD Treatment
journal, September 2019

  • Young, Matthias J.; Letourneau, Steven; Warburton, Robert E.
  • The Journal of Physical Chemistry C, Vol. 123, Issue 39
  • DOI: 10.1021/acs.jpcc.9b04418

Chemical Reactivity Descriptor for the Oxide-Electrolyte Interface in Li-Ion Batteries
journal, August 2017

  • Giordano, Livia; Karayaylali, Pinar; Yu, Yang
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 16
  • DOI: 10.1021/acs.jpclett.7b01655

Oxidation States of Mn Atoms at Clean and Al 2 O 3 -Covered LiMn 2 O 4 (001) Surfaces
journal, March 2010

  • Ouyang, C. Y.; Zeng, X. M.; Šljivancanin, Ž.
  • The Journal of Physical Chemistry C, Vol. 114, Issue 10
  • DOI: 10.1021/jp911746g

Band Diagram and Rate Analysis of Thin Film Spinel LiMn 2 O 4 Formed by Electrochemical Conversion of ALD-Grown MnO
journal, September 2016

  • Young, Matthias J.; Schnabel, Hans-Dieter; Holder, Aaron M.
  • Advanced Functional Materials, Vol. 26, Issue 43
  • DOI: 10.1002/adfm.201602773

First-Principles Modeling of the Initial Stages of Organic Solvent Decomposition on Li x Mn 2 O 4 (100) Surfaces
journal, April 2012

  • Leung, Kevin
  • The Journal of Physical Chemistry C, Vol. 116, Issue 18
  • DOI: 10.1021/jp212415x

Effect of AlF3 coating amount on high voltage cycling performance of LiCoO2
journal, December 2007


Lithium transport through lithium-ion battery cathode coatings
journal, January 2015

  • Xu, Shenzhen; Jacobs, Ryan M.; Nguyen, Ha M.
  • Journal of Materials Chemistry A, Vol. 3, Issue 33
  • DOI: 10.1039/C5TA01664A

Reaction of Trimethylaluminum with Water on Pt(111) and Pd(111) from 10 –5 to 10 –1 Millibar
journal, January 2015

  • Detwiler, Michael D.; Gharachorlou, Amir; Mayr, Lukas
  • The Journal of Physical Chemistry C
  • DOI: 10.1021/jp510032u

Charge Storage in Cation Incorporated α-MnO 2
journal, February 2015

  • Young, Matthias J.; Holder, Aaron M.; George, Steven M.
  • Chemistry of Materials, Vol. 27, Issue 4
  • DOI: 10.1021/cm503544e

Self-Discharge of LiMn[sub 2]O[sub 4]/C Li-Ion Cells in Their Discharged State
journal, January 1998

  • Blyr, A.
  • Journal of The Electrochemical Society, Vol. 145, Issue 1
  • DOI: 10.1149/1.1838235

Atomic Layer Deposition: An Overview
journal, January 2010

  • George, Steven M.
  • Chemical Reviews, Vol. 110, Issue 1, p. 111-131
  • DOI: 10.1021/cr900056b

Strategies for improving the cyclability and thermo-stability of LiMn 2 O 4 -based batteries at elevated temperatures
journal, January 2015

  • Xu, Gaojie; Liu, Zhihong; Zhang, Chuanjian
  • Journal of Materials Chemistry A, Vol. 3, Issue 8
  • DOI: 10.1039/C4TA06264G

Atomic Layer Deposition of Al–W–Fluoride on LiCoO 2 Cathodes: Comparison of Particle- and Electrode-Level Coatings
journal, July 2017


Crystallinity of inorganic films grown by atomic layer deposition: Overview and general trends
journal, January 2013

  • Miikkulainen, Ville; Leskelä, Markku; Ritala, Mikko
  • Journal of Applied Physics, Vol. 113, Issue 2, Article No. 021301
  • DOI: 10.1063/1.4757907

Influence of manganese(II), cobalt(II), and nickel(II) additives in electrolyte on performance of graphite anode for lithium-ion batteries
journal, February 2002


Structure–activity relationships for propane oxidative dehydrogenation by anatase-supported vanadium oxide monomers and dimers
journal, June 2013


Enhancement of Li-ion battery performance of graphite anode by sodium ion as an electrolyte additive
journal, November 2003


Oxidation energies of transition metal oxides within the GGA + U framework
journal, May 2006


Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points
journal, December 2000

  • Henkelman, Graeme; Jónsson, Hannes
  • The Journal of Chemical Physics, Vol. 113, Issue 22
  • DOI: 10.1063/1.1323224

Simulation of Aqueous Dissolution of Lithium Manganate Spinel from First Principles
journal, February 2012

  • Benedek, R.; Thackeray, M. M.; Low, J.
  • The Journal of Physical Chemistry C, Vol. 116, Issue 6
  • DOI: 10.1021/jp208793k

Preparation and characterization of gold-codeposited LiMn2O4 electrodes
journal, January 2001


Ultrathin Lithium-Ion Conducting Coatings for Increased Interfacial Stability in High Voltage Lithium-Ion Batteries
journal, May 2014

  • Park, Joong Sun; Meng, Xiangbo; Elam, Jeffrey W.
  • Chemistry of Materials, Vol. 26, Issue 10
  • DOI: 10.1021/cm500512n

Mechanisms of LiCoO 2 Cathode Degradation by Reaction with HF and Protection by Thin Oxide Coatings
journal, October 2015

  • Tebbe, Jonathon L.; Holder, Aaron M.; Musgrave, Charles B.
  • ACS Applied Materials & Interfaces, Vol. 7, Issue 43
  • DOI: 10.1021/acsami.5b07887