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This content will become publicly available on March 7, 2019

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

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.
 [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:
Grant/Contract Number:
Accepted Manuscript
Journal Name:
Advanced Materials Interfaces
Additional Journal Information:
Journal Volume: 5; Journal Issue: 10; Journal ID: ISSN 2196-7350
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States); Univ. of Illinois at Urbana-Champaign, IL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
25 ENERGY STORAGE; alkylphosphonate; lithium-ion battery cathode; lithium manganese oxide; self-assembled monolayers; surface modification
OSTI Identifier:
Alternate Identifier(s):
OSTI ID: 1424518