Controlling Interfacial Properties of Lithium-Ion Battery Cathodes with Alkylphosphonate Self-Assembled Monolayers
Abstract
Abstract In this work, the preparation and characterization of modified LiMn 2 O 4 (LMO) cathodes utilizing chemisorbed alkylphosphonic acids to chemically modify their surfaces are reported. Electrochemical methods to study ionic and molecular mobility through the alkylphosphonate self‐assembled monolayers (SAMs) for different alkyl chain compositions, in order to better understand their impact on the lithium‐ion electrochemistry, are utilized. Electrochemical trends for different chains correlate to trends observed in contact angle measurements and solvation energies obtained from computational methods, indicating that attributes of the microscopic wettability of these interfaces with the battery electrolyte have an important impact on ionic mobility. The effects of surface modification on Mn dissolution are also reported. The alkylphosphonate layer provides an important mode of chemical stabilization to the LMO, suppressing Mn dissolution by 90% during extended immersion in electrolytes. A more modest reduction in dissolution is found upon galvanostatic cycling, in comparison to pristine LMO cathodes. Taken together, the data suggest that alkylphosphonates provide a versatile means for the surface modification of lithium‐ion battery cathode materials allowing the design of specific interfaces through modification of organic chain functionalities.
- Authors:
-
- Univ. of Illinois, Urbana, IL (United States). Dept. of Chemistry
- Argonne National Lab. (ANL), Argonne, IL (United States). Center for Nanoscale Materials
- Argonne National Lab. (ANL), Argonne, IL (United States). Argonne Leadership Computing Facility
- Univ. of Illinois, Urbana, IL (United States). Frederick Seitz Materials Research Lab.
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States); Univ. of Illinois at Urbana-Champaign, IL (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Electrical Energy Storage (CEES)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1461434
- Alternate Identifier(s):
- OSTI ID: 1424518
- Grant/Contract Number:
- AC02-06CH11357; DE‐AC02‐06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Advanced Materials Interfaces
- Additional Journal Information:
- Journal Volume: 5; Journal Issue: 10; Journal ID: ISSN 2196-7350
- Publisher:
- Wiley-VCH
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; alkylphosphonate; lithium-ion battery cathode; lithium manganese oxide; self-assembled monolayers; surface modification
Citation Formats
Nicolau, Bruno G., Petronico, Aaron, Letchworth-Weaver, Kendra, Ghadar, Yasaman, Haasch, Richard T., Soares, Julio A. N. T., Rooney, Ryan T., Chan, Maria K. Y., Gewirth, Andrew A., and Nuzzo, Ralph G. Controlling Interfacial Properties of Lithium-Ion Battery Cathodes with Alkylphosphonate Self-Assembled Monolayers. United States: N. p., 2018.
Web. doi:10.1002/admi.201701292.
Nicolau, Bruno G., Petronico, Aaron, Letchworth-Weaver, Kendra, Ghadar, Yasaman, Haasch, Richard T., Soares, Julio A. N. T., Rooney, Ryan T., Chan, Maria K. Y., Gewirth, Andrew A., & Nuzzo, Ralph G. Controlling Interfacial Properties of Lithium-Ion Battery Cathodes with Alkylphosphonate Self-Assembled Monolayers. United States. https://doi.org/10.1002/admi.201701292
Nicolau, Bruno G., Petronico, Aaron, Letchworth-Weaver, Kendra, Ghadar, Yasaman, Haasch, Richard T., Soares, Julio A. N. T., Rooney, Ryan T., Chan, Maria K. Y., Gewirth, Andrew A., and Nuzzo, Ralph G. Wed .
"Controlling Interfacial Properties of Lithium-Ion Battery Cathodes with Alkylphosphonate Self-Assembled Monolayers". United States. https://doi.org/10.1002/admi.201701292. https://www.osti.gov/servlets/purl/1461434.
@article{osti_1461434,
title = {Controlling Interfacial Properties of Lithium-Ion Battery Cathodes with Alkylphosphonate Self-Assembled Monolayers},
author = {Nicolau, Bruno G. and Petronico, Aaron and Letchworth-Weaver, Kendra and Ghadar, Yasaman and Haasch, Richard T. and Soares, Julio A. N. T. and Rooney, Ryan T. and Chan, Maria K. Y. and Gewirth, Andrew A. and Nuzzo, Ralph G.},
abstractNote = {Abstract In this work, the preparation and characterization of modified LiMn 2 O 4 (LMO) cathodes utilizing chemisorbed alkylphosphonic acids to chemically modify their surfaces are reported. Electrochemical methods to study ionic and molecular mobility through the alkylphosphonate self‐assembled monolayers (SAMs) for different alkyl chain compositions, in order to better understand their impact on the lithium‐ion electrochemistry, are utilized. Electrochemical trends for different chains correlate to trends observed in contact angle measurements and solvation energies obtained from computational methods, indicating that attributes of the microscopic wettability of these interfaces with the battery electrolyte have an important impact on ionic mobility. The effects of surface modification on Mn dissolution are also reported. The alkylphosphonate layer provides an important mode of chemical stabilization to the LMO, suppressing Mn dissolution by 90% during extended immersion in electrolytes. A more modest reduction in dissolution is found upon galvanostatic cycling, in comparison to pristine LMO cathodes. Taken together, the data suggest that alkylphosphonates provide a versatile means for the surface modification of lithium‐ion battery cathode materials allowing the design of specific interfaces through modification of organic chain functionalities.},
doi = {10.1002/admi.201701292},
journal = {Advanced Materials Interfaces},
number = 10,
volume = 5,
place = {United States},
year = {Wed Mar 07 00:00:00 EST 2018},
month = {Wed Mar 07 00:00:00 EST 2018}
}
Web of Science
Figures / Tables:
Works referenced in this record:
Constant pressure molecular dynamics for molecular systems
journal, December 1983
- Nosé, Shuichi; Klein, M. L.
- Molecular Physics, Vol. 50, Issue 5
Electrochemical studies of ferrocene in a lithium ion conducting organic carbonate electrolyte
journal, November 2009
- Laoire, Cormac O.; Plichta, Edward; Hendrickson, Mary
- Electrochimica Acta, Vol. 54, Issue 26
Computer "Experiments" on Classical Fluids. I. Thermodynamical Properties of Lennard-Jones Molecules
journal, July 1967
- Verlet, Loup
- Physical Review, Vol. 159, Issue 1
Issues and challenges facing rechargeable lithium batteries
journal, November 2001
- Tarascon, J.-M.; Armand, M.
- Nature, Vol. 414, Issue 6861, p. 359-367
Simple models for hydrophobic hydration
journal, January 2005
- Höfinger, Siegfried; Zerbetto, Francesco
- Chemical Society Reviews, Vol. 34, Issue 12
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
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
Development of thin film cathodes for lithium-ion batteries in the material system Li–Mn–O by r.f. magnetron sputtering
journal, January 2013
- Fischer, J.; Adelhelm, C.; Bergfeldt, T.
- Thin Solid Films, Vol. 528
The Surface Structure of the Proton-Exchanged Lithium Manganese Oxide Spinels and Their Lithium-Ion Sieve Properties
journal, June 1997
- Sato, K.; Poojary, D. M.; Clearfield, A.
- Journal of Solid State Chemistry, Vol. 131, Issue 1
Theoretical study of the surface modification of indium tin oxide with trifluorophenyl phosphonic acid molecules: impact of coverage density and binding geometry
journal, January 2010
- Li, Hong; Paramonov, Pavel; Bredas, Jean-Luc
- Journal of Materials Chemistry, Vol. 20, Issue 13
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
Experimental and ab initio investigations on textured Li–Mn–O spinel thin film cathodes
journal, December 2014
- Fischer, J.; Music, D.; Bergfeldt, T.
- Thin Solid Films, Vol. 572
Sub-2 nm Thick Fluoroalkylsilane Self-Assembled Monolayer-Coated High Voltage Spinel Crystals as Promising Cathode Materials for Lithium Ion Batteries
journal, August 2016
- Zettsu, Nobuyuki; Kida, Satoru; Uchida, Shuhei
- Scientific Reports, Vol. 6, Issue 1
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
Influence of annealing temperature on microstructural and electrochemical properties of rf-sputtered LiMn2O4 film cathodes
journal, June 2012
- Jayanth-Babu, K.; Jeevan-Kumar, P.; Hussain, O. M.
- Journal of Solid State Electrochemistry, Vol. 16, Issue 10
Phosphonic Acids for Interfacial Engineering of Transparent Conductive Oxides
journal, May 2016
- Paniagua, Sergio A.; Giordano, Anthony J.; Smith, O’Neil L.
- Chemical Reviews, Vol. 116, Issue 12
Ab initio molecular-orbital study on the surface reactions of methane and silane plasma chemical vapor deposition
journal, June 1997
- Sato, Kota; Haruta, Hitoshi; Kumashiro, Yukinobu
- Physical Review B, Vol. 55, Issue 23
Electrochemical features of ball-milled lithium manganate spinel for rapid-charge cathodes of lithium ion batteries
journal, February 2012
- Crain, Daniel; Zheng, Jianping; Sulyma, Christopher
- Journal of Solid State Electrochemistry, Vol. 16, Issue 8
Quantitative Analysis and Characterization of DNA Immobilized on Gold
journal, April 2003
- Petrovykh, Dmitri Y.; Kimura-Suda, Hiromi; Whitman, Lloyd J.
- Journal of the American Chemical Society, Vol. 125, Issue 17
Thin films of lithium manganese oxide spinel as cathode materials for secondary lithium batteries
journal, May 2004
- Shui, J. L.; Jiang, G. S.; Xie, S.
- Electrochimica Acta, Vol. 49, Issue 13
Surface Modification Using Phosphonic Acids and Esters
journal, April 2012
- Queffélec, Clémence; Petit, Marc; Janvier, Pascal
- Chemical Reviews, Vol. 112, Issue 7
Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries
journal, October 2004
- Xu, Kang
- Chemical Reviews, Vol. 104, Issue 10, p. 4303-4418
Poly(dG) Spacers Lead to Increased Surface Coverage of DNA Probes: An XPS Study of Oligonucleotide Binding to Zirconium Phosphonate Modified Surfaces
journal, July 2008
- Lane, Sarah M.; Monot, Julien; Petit, Marc
- Langmuir, Vol. 24, Issue 14
Electrical transport properties in LiMn2O4, Li0.95Mn2O4, and LiMn1.95B0.05O4 (B=Al or Ga) around room temperature
journal, February 2002
- Iguchi, E.; Tokuda, Y.; Nakatsugawa, H.
- Journal of Applied Physics, Vol. 91, Issue 4
Electrochemical characterization of self-assembled monolayers on gold substrates derived from thermal decomposition of monolayer-protected cluster films
journal, August 2015
- Leopold, Michael C.; Doan, Tran T.; Mullaney, Melissa J.
- Journal of Applied Electrochemistry, Vol. 45, Issue 10
A unified formulation of the constant temperature molecular dynamics methods
journal, July 1984
- Nosé, Shuichi
- The Journal of Chemical Physics, Vol. 81, Issue 1
Effect of Mn and Cu Addition on Lithiation and SEI Formation on Model Anode Electrodes
journal, January 2014
- Esbenshade, Jennifer L.; Gewirth, Andrew A.
- Journal of The Electrochemical Society, Vol. 161, Issue 4
Long Distance Electron Transfer at the Metal/Alkanethiol/Ionic Liquid Interface
journal, July 2014
- Nikitina, Victoria A.; Rudnev, Alexander V.; Tsirlina, Galina A.
- The Journal of Physical Chemistry C, Vol. 118, Issue 29
Joint Density-Functional Theory: Ab Initio Study of Cr 2 O 3 Surface Chemistry in Solution
journal, August 2005
- Petrosyan, S. A.; Rigos, A. A.; Arias, T. A.
- The Journal of Physical Chemistry B, Vol. 109, Issue 32
Studies on LiFePO4 as cathode material using impedance spectroscopy
journal, June 2011
- Schmidt, Jan Philipp; Chrobak, Thorsten; Ender, Moses
- Journal of Power Sources, Vol. 196, Issue 12
Adsorption studies of a phosphonic acid on ITO: film coverage, purity, and induced electronic structure changes
journal, January 2014
- Paniagua, S. A.; Li, E. L.; Marder, S. R.
- Physical Chemistry Chemical Physics, Vol. 16, Issue 7
A review of the features and analyses of the solid electrolyte interphase in Li-ion batteries
journal, September 2010
- Verma, Pallavi; Maire, Pascal; Novák, Petr
- Electrochimica Acta, Vol. 55, Issue 22, p. 6332-6341
Lithium Manganese Oxide (LiMn2O4) by XPS
journal, July 2001
- Militello, Maria C.; Gaarenstroom, Stephen W.
- Surface Science Spectra, Vol. 8, Issue 3
The Modification of Indium Tin Oxide with Phosphonic Acids: Mechanism of Binding, Tuning of Surface Properties, and Potential for Use in Organic Electronic Applications
journal, October 2011
- Hotchkiss, Peter J.; Jones, Simon C.; Paniagua, Sergio A.
- Accounts of Chemical Research, Vol. 45, Issue 3
Interfacial Processes of a Model Lithium Ion Battery Anode Observed, in Situ, with Vibrational Sum-Frequency Generation Spectroscopy
journal, May 2015
- Nicolau, Bruno G.; Garcı́a-Rey, Natalia; Dryzhakov, Bogdan
- The Journal of Physical Chemistry C, Vol. 119, Issue 19
Characterization of the Cathode Electrolyte Interface in Lithium Ion Batteries by Desorption Electrospray Ionization Mass Spectrometry
journal, July 2016
- Liu, Yao-Min; G. Nicolau, Bruno; Esbenshade, Jennifer L.
- Analytical Chemistry, Vol. 88, Issue 14
Identification of lithium–sulfur battery discharge products through 6Li and 33S solid-state MAS and 7Li solution NMR spectroscopy
journal, January 2015
- Huff, Laura A.; Rapp, Jennifer L.; Baughman, Jessi A.
- Surface Science, Vol. 631
The importance of nonlinear fluid response in joint density-functional theory studies of battery systems
journal, October 2013
- Gunceler, Deniz; Letchworth-Weaver, Kendra; Sundararaman, Ravishankar
- Modelling and Simulation in Materials Science and Engineering, Vol. 21, Issue 7
Low adhesion, non-wetting phosphonate self-assembled monolayer films formed on copper oxide surfaces
journal, July 2009
- Hoque, E.; DeRose, J. A.; Bhushan, B.
- Ultramicroscopy, Vol. 109, Issue 8
Understanding the electronic and ionic conduction and lithium over-stoichiometry in LiMn 2 O 4 spinel
journal, January 2014
- Hoang, Khang
- J. Mater. Chem. A, Vol. 2, Issue 43
Canonical dynamics: Equilibrium phase-space distributions
journal, March 1985
- Hoover, William G.
- Physical Review A, Vol. 31, Issue 3
Effect of bulk structure of some non-aqueous solvents on the barrier properties of alkanethiol monolayer
journal, December 2001
- Sur, Ujjal Kumar; Lakshminarayanan, V.
- Journal of Electroanalytical Chemistry, Vol. 516, Issue 1-2
The Formation Mechanism of Fluorescent Metal Complexes at the Li x Ni 0.5 Mn 1.5 O 4−δ /Carbonate Ester Electrolyte Interface
journal, March 2015
- Jarry, Angélique; Gottis, Sébastien; Yu, Young-Sang
- Journal of the American Chemical Society, Vol. 137, Issue 10
Improvement of electrochemical stability of LiMn2O4 by CeO2 coating for lithium-ion batteries
journal, February 2007
- Ha, Hyung-Wook; Yun, Nan Ji; Kim, Keon
- Electrochimica Acta, Vol. 52, Issue 9
Phosphonic Acid Modification of Indium−Tin Oxide Electrodes: Combined XPS/UPS/Contact Angle Studies
journal, April 2008
- Paniagua, Sergio A.; Hotchkiss, Peter J.; Jones, Simon C.
- The Journal of Physical Chemistry C, Vol. 112, Issue 21
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
XPS investigation of DNA binding to zirconium-phosphonate surfaces
journal, July 2007
- Lane, Sarah M.; Monot, Julien; Petit, Marc
- Colloids and Surfaces B: Biointerfaces, Vol. 58, Issue 1
Covalent Surface Modification of Oxide Surfaces
journal, May 2014
- Pujari, Sidharam P.; Scheres, Luc; Marcelis, Antonius T. M.
- Angewandte Chemie International Edition, Vol. 53, Issue 25
Electrochemical characterization of Self-assembled Monolayers (SAMs) of silanes on indium tin oxide (ITO) electrodes – Tuning electron transfer behaviour across electrode–electrolyte interface
journal, May 2012
- Muthurasu, A.; Ganesh, V.
- Journal of Colloid and Interface Science, Vol. 374, Issue 1
Investigation on Surface-Film Formation Behavior of LiMn 2 O 4 Thin-Film Electrodes in LiClO 4 /Propylene Carbonate
journal, April 2017
- Inamoto, Jun-ichi; Fukutsuka, Tomokazu; Miyazaki, Kohei
- ChemistrySelect, Vol. 2, Issue 10
Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries
journal, December 2004
- Xu, Kang
- ChemInform, Vol. 35, Issue 50
Voltage- and time-dependent valence state transition in cobalt oxide catalysts during the oxygen evolution reaction
journal, April 2020
- Zhou, Jing; Zhang, Linjuan; Huang, Yu-Cheng
- Nature Communications, Vol. 11, Issue 1
Amorphization-induced surface electronic states modulation of cobaltous oxide nanosheets for lithium-sulfur batteries
journal, May 2021
- Li, Ruilong; Rao, Dewei; Zhou, Jianbin
- Nature Communications, Vol. 12, Issue 1
Simple Models for Hydrophobic Hydration
journal, March 2006
- Hoefinger, Siegfried; Zerbetto, Francesco
- ChemInform, Vol. 37, Issue 11
The importance of nonlinear fluid response in joint density-functional theory studies of battery systems
text, January 2013
- Gunceler, Deniz; Letchworth-Weaver, Kendra; Sundararaman, Ravishankar
- arXiv
Understanding the electronic and ionic conduction and lithium over-stoichiometry in LiMn$_2$O$_4$ spinel
text, January 2014
- Hoang, Khang
- arXiv
Works referencing / citing this record:
Synthesis and Electrochemical Performance of Cobalt-Doped KMnF 3 as Cathode Materials for Potassium Ion Batteries
journal, January 2019
- Wang, Shuya; Cui, Bin; Zhuang, Quanchao
- Journal of The Electrochemical Society, Vol. 166, Issue 10
Scalable Synthesis Nano-Perovskite K(Mn0.95Ni0.05)F3 Cathode by Homogeneous Precipitation Method for Potassium-Ion Batteries
journal, July 2019
- Wang, Shuya; Cui, Bin; Zhuang, Quanchao
- Nanoscale Research Letters, Vol. 14, Issue 1
Figures / Tables found in this record: