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

Abstract

In this paper, the preparation and characterization of modified LiMn 2O 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. Finally, 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:
 [1];  [1];  [2];  [3];  [4];  [4];  [1];  [2]; ORCiD logo [1];  [1]
  1. Univ. of Illinois, Urbana, IL (United States). Dept. of Chemistry
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Center for Nanoscale Materials
  3. Argonne National Lab. (ANL), Argonne, IL (United States). Argonne Leadership Computing Facility
  4. Univ. of Illinois, Urbana, IL (United States). Frederick Seitz Materials Research Lab.
Publication Date:
Research Org.:
Argonne National Lab. (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) (SC-22)
OSTI Identifier:
1461434
Alternate Identifier(s):
OSTI ID: 1424518
Grant/Contract Number:  
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. 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., and Nuzzo, Ralph G. Wed . "Controlling Interfacial Properties of Lithium-Ion Battery Cathodes with Alkylphosphonate Self-Assembled Monolayers". United States. doi: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 = {In this paper, 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. Finally, 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 = {2018},
month = {3}
}

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Figures / Tables:

Figure 1 Figure 1: Cyclic voltammetry measurements of alkylphosphonate-modified LiMn2O4 thin films in 1 M LiClO4 in PC electrolyte (with added 3 mM ferrocene) measured at a scan rate of 0.2 mV/s. Two different redox pairs are observed, containing information about the ferrocene oxidation (region 1) and lithiation/delithiation (region 2).

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