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Title: In-situ/operando X-ray absorption spectroscopic investigation of the electrode/electrolyte interface on the molecular scale

Abstract

A method for performing X-ray absorption spectroscopy (XAS) in the soft X-ray region was developed to investigate the surface-sensitive electron signal of electrode/electrolyte interfaces in common multivalent based organic solvents under in situ/operando conditions. Our approach enables us to probe the molecular-scale structure of electrode interfaces by measuring total electron yield and is suitable for redox systems exhibiting low intrinsic electrochemical current. In-situ F K-edge XAS measurements in a 0.5 M Magnesium bis(trifluoromethanesulfonimide)/2-Methyltetrahydrofuran (Mg(TFSI)2/2-MeTHF) electrolyte were carried out to determine the evolution of interfacial species during the electrochemical charging/discharging process. Time-dependent density-functional theory (TD-DFT) simulation indicate that the F K-edge evolution is the result of interfacial chemical environment change driven by electrochemical potential. In addition, we performed the “operando XAS” which runs the CV and collects spectra simultaneously. Furthermore, by using this method, the non-equilibrium state of condensed matter interfaces and interfacial dynamical transient process can be revealed.

Authors:
 [1];  [2];  [1];  [2];  [1];  [3];  [1];  [1];  [1];  [3];  [4]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Joint Center for Energy Storage Research, Lemont, IL (United States)
  3. Joint Center for Energy Storage Research, Lemont, IL (United States); Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Joint Center for Energy Storage Research, Lemont, IL (United States); Univ. of California, Santa Cruz, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1838426
Alternate Identifier(s):
OSTI ID: 1776224
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Surface Science
Additional Journal Information:
Journal Volume: 702; Journal ID: ISSN 0039-6028
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; In-situ/operando; Soft X-ray; XAS; Interface; Battery

Citation Formats

Kao, Li Cheng, Feng, Xuefei, Ha, Yang, Yang, Feipeng, Liu, Yi-Sheng, Hahn, Nathan T., MacDougall, James, Chao, Weilun, Yang, Wanli, Zavadil, Kevin R., and Guo, Jinghua. In-situ/operando X-ray absorption spectroscopic investigation of the electrode/electrolyte interface on the molecular scale. United States: N. p., 2020. Web. doi:10.1016/j.susc.2020.121720.
Kao, Li Cheng, Feng, Xuefei, Ha, Yang, Yang, Feipeng, Liu, Yi-Sheng, Hahn, Nathan T., MacDougall, James, Chao, Weilun, Yang, Wanli, Zavadil, Kevin R., & Guo, Jinghua. In-situ/operando X-ray absorption spectroscopic investigation of the electrode/electrolyte interface on the molecular scale. United States. https://doi.org/10.1016/j.susc.2020.121720
Kao, Li Cheng, Feng, Xuefei, Ha, Yang, Yang, Feipeng, Liu, Yi-Sheng, Hahn, Nathan T., MacDougall, James, Chao, Weilun, Yang, Wanli, Zavadil, Kevin R., and Guo, Jinghua. Sun . "In-situ/operando X-ray absorption spectroscopic investigation of the electrode/electrolyte interface on the molecular scale". United States. https://doi.org/10.1016/j.susc.2020.121720. https://www.osti.gov/servlets/purl/1838426.
@article{osti_1838426,
title = {In-situ/operando X-ray absorption spectroscopic investigation of the electrode/electrolyte interface on the molecular scale},
author = {Kao, Li Cheng and Feng, Xuefei and Ha, Yang and Yang, Feipeng and Liu, Yi-Sheng and Hahn, Nathan T. and MacDougall, James and Chao, Weilun and Yang, Wanli and Zavadil, Kevin R. and Guo, Jinghua},
abstractNote = {A method for performing X-ray absorption spectroscopy (XAS) in the soft X-ray region was developed to investigate the surface-sensitive electron signal of electrode/electrolyte interfaces in common multivalent based organic solvents under in situ/operando conditions. Our approach enables us to probe the molecular-scale structure of electrode interfaces by measuring total electron yield and is suitable for redox systems exhibiting low intrinsic electrochemical current. In-situ F K-edge XAS measurements in a 0.5 M Magnesium bis(trifluoromethanesulfonimide)/2-Methyltetrahydrofuran (Mg(TFSI)2/2-MeTHF) electrolyte were carried out to determine the evolution of interfacial species during the electrochemical charging/discharging process. Time-dependent density-functional theory (TD-DFT) simulation indicate that the F K-edge evolution is the result of interfacial chemical environment change driven by electrochemical potential. In addition, we performed the “operando XAS” which runs the CV and collects spectra simultaneously. Furthermore, by using this method, the non-equilibrium state of condensed matter interfaces and interfacial dynamical transient process can be revealed.},
doi = {10.1016/j.susc.2020.121720},
journal = {Surface Science},
number = ,
volume = 702,
place = {United States},
year = {Sun Aug 23 00:00:00 EDT 2020},
month = {Sun Aug 23 00:00:00 EDT 2020}
}

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