Controlling Interfacial Properties of Lithium-Ion Battery Cathodes with Alkylphosphonate Self-Assembled Monolayers

Bruno G. Nicolau; Aaron Petronico; Kendra Letchworth-Weaver; Yasaman Ghadar; Richard T. Haasch; Julio A.N.T. Soares; Ryan T. Rooney; Maria K.Y. Chan; Andrew A. Gewirth; Ralph G. Nuzzo

doi:10.1002/admi.201701292

Controlling Interfacial Properties of Lithium-Ion Battery Cathodes with Alkylphosphonate Self-Assembled Monolayers

Bruno G. Nicolau, Aaron Petronico, Kendra Letchworth-Weaver, Yasaman Ghadar, Richard T. Haasch, Julio A.N.T. Soares, Ryan T. Rooney, Maria K.Y. Chan, Andrew A. Gewirth^*, Ralph G. Nuzzo

^*Corresponding author for this work

MRC - Materials Research Center

Research output: Contribution to journal › Article › peer-review

26 Scopus citations

Abstract

In this work, the preparation and characterization of modified LiMn₂O₄ (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.

Original language	English (US)
Article number	1701292
Journal	Advanced Materials Interfaces
Volume	5
Issue number	10
DOIs	https://doi.org/10.1002/admi.201701292
State	Published - May 23 2018

Funding

B.G.N. thanks Kimberly L. Basset for assistance and discussion about the work carried out with RF Sputtering deposition of LMO. Dr. Lingzi Sang provided very helpful advice about the alkylphosphonate systems and possible methods of characterization of the modified LMO surfaces. This research was supported as a part of the Center for Electrical Energy Science, an Energy Frontier Research Center funded by the U.S. Department of Energy. This work was carried out in part in the Frederick Seitz Materials Research Laboratory Central Facilities. Use of the Center for Nanoscale Materials, an Office of Science user facility, was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. This research used resources of the Argonne Leadership Computing Facility, which is a DOE Office of Science User Facility supported under Contract No. DE-AC02-06CH11357.

Keywords

alkylphosphonate
lithium manganese oxide
lithium-ion battery cathode
self-assembled monolayers
surface modification

ASJC Scopus subject areas

Mechanics of Materials
Mechanical Engineering

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.1002/admi.201701292

Cite this

Nicolau, B. G., Petronico, A., Letchworth-Weaver, K., Ghadar, Y., Haasch, R. T., Soares, J. A. N. T., Rooney, R. T., Chan, M. K. Y., Gewirth, A. A., & Nuzzo, R. G. (2018). Controlling Interfacial Properties of Lithium-Ion Battery Cathodes with Alkylphosphonate Self-Assembled Monolayers. Advanced Materials Interfaces, 5(10), Article 1701292. https://doi.org/10.1002/admi.201701292

@article{92537e411691429a9b176f859628c5fd,

title = "Controlling Interfacial Properties of Lithium-Ion Battery Cathodes with Alkylphosphonate Self-Assembled Monolayers",

abstract = "In this work, the preparation and characterization of modified LiMn2O4 (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.",

keywords = "alkylphosphonate, lithium manganese oxide, lithium-ion battery cathode, self-assembled monolayers, surface modification",

author = "Nicolau, {Bruno G.} and Aaron Petronico and Kendra Letchworth-Weaver and Yasaman Ghadar 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.}",

note = "Funding Information: B.G.N. thanks Kimberly L. Basset for assistance and discussion about the work carried out with RF Sputtering deposition of LMO. Dr. Lingzi Sang provided very helpful advice about the alkylphosphonate systems and possible methods of characterization of the modified LMO surfaces. This research was supported as a part of the Center for Electrical Energy Science, an Energy Frontier Research Center funded by the U.S. Department of Energy. This work was carried out in part in the Frederick Seitz Materials Research Laboratory Central Facilities. Use of the Center for Nanoscale Materials, an Office of Science user facility, was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. This research used resources of the Argonne Leadership Computing Facility, which is a DOE Office of Science User Facility supported under Contract No. DE-AC02-06CH11357. Publisher Copyright: {\textcopyright} 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2018",

month = may,

day = "23",

doi = "10.1002/admi.201701292",

language = "English (US)",

volume = "5",

journal = "Advanced Materials Interfaces",

issn = "2196-7350",

publisher = "John Wiley and Sons Ltd",

number = "10",

}

TY - JOUR

T1 - Controlling Interfacial Properties of Lithium-Ion Battery Cathodes with Alkylphosphonate Self-Assembled Monolayers

AU - Nicolau, Bruno G.

AU - Petronico, Aaron

AU - Letchworth-Weaver, Kendra

AU - Ghadar, Yasaman

AU - Haasch, Richard T.

AU - Soares, Julio A.N.T.

AU - Rooney, Ryan T.

AU - Chan, Maria K.Y.

AU - Gewirth, Andrew A.

AU - Nuzzo, Ralph G.

N1 - Funding Information: B.G.N. thanks Kimberly L. Basset for assistance and discussion about the work carried out with RF Sputtering deposition of LMO. Dr. Lingzi Sang provided very helpful advice about the alkylphosphonate systems and possible methods of characterization of the modified LMO surfaces. This research was supported as a part of the Center for Electrical Energy Science, an Energy Frontier Research Center funded by the U.S. Department of Energy. This work was carried out in part in the Frederick Seitz Materials Research Laboratory Central Facilities. Use of the Center for Nanoscale Materials, an Office of Science user facility, was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. This research used resources of the Argonne Leadership Computing Facility, which is a DOE Office of Science User Facility supported under Contract No. DE-AC02-06CH11357. Publisher Copyright: © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2018/5/23

Y1 - 2018/5/23

N2 - In this work, the preparation and characterization of modified LiMn2O4 (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.

AB - In this work, the preparation and characterization of modified LiMn2O4 (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.

KW - alkylphosphonate

KW - lithium manganese oxide

KW - lithium-ion battery cathode

KW - self-assembled monolayers

KW - surface modification

UR - http://www.scopus.com/inward/record.url?scp=85043368111&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85043368111&partnerID=8YFLogxK

U2 - 10.1002/admi.201701292

DO - 10.1002/admi.201701292

M3 - Article

AN - SCOPUS:85043368111

SN - 2196-7350

VL - 5

JO - Advanced Materials Interfaces

JF - Advanced Materials Interfaces

IS - 10

M1 - 1701292

ER -

Controlling Interfacial Properties of Lithium-Ion Battery Cathodes with Alkylphosphonate Self-Assembled Monolayers

Abstract

Funding

Keywords

ASJC Scopus subject areas

UN SDGs

Access to Document

Other files and links

Fingerprint

Cite this