skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

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

Journal Article · · Surface Science
 [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)
+ Show Author Affiliations

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.

Research Organization:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1838426
Alternate ID(s):
OSTI ID: 1776224
Journal Information:
Surface Science, Vol. 702; ISSN 0039-6028
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English

References (39)

Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy journal January 2005
Introducing Ionic-Current Detection for X-ray Absorption Spectroscopy in Liquid Cells journal April 2017
Magnesium Borohydride: From Hydrogen Storage to Magnesium Battery journal August 2012
Deciphering the Solvent Effect for the Solvation Structure of Ca 2+ in Polar Molecular Liquids journal March 2020
Avoiding pitfalls in the modeling of electrochemical interfaces journal January 2013
Novel spectro-electrochemical cell for in situ / operando observation of common composite electrode with liquid electrolyte by X-ray absorption spectroscopy in the tender X-ray region journal August 2014
Predicting Phosphorescence Rates of Light Organic Molecules Using Time-Dependent Density Functional Theory and the Path Integral Approach to Dynamics journal February 2019
Review—Development of Advanced Rechargeable Batteries: A Continuous Challenge in the Choice of Suitable Electrolyte Solutions journal January 2015
First-Principles Molecular Dynamics at a Constant Electrode Potential journal December 2012
A perfluorinated moiety-grafted carbon nanotube electrode for the non-aqueous lithium–oxygen battery journal January 2015
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density journal January 1988
X-ray-Induced Fragmentation of Imidazolium-Based Ionic Liquids Studied by Soft X-ray Absorption Spectroscopy journal February 2018
Frontiers of in situ electron microscopy journal January 2015
Tracking the Chemical and Structural Evolution of the TiS 2 Electrode in the Lithium-Ion Cell Using Operando X-ray Absorption Spectroscopy journal June 2018
Electrochemical Reaction of Aqueous Iron Sulfate Solutions Studied by Fe L-Edge Soft X-ray Absorption Spectroscopy journal August 2013
The structure of interfacial water on gold electrodes studied by x-ray absorption spectroscopy journal October 2014
Molecular-Scale Structure of Electrode–Electrolyte Interfaces: The Case of Platinum in Aqueous Sulfuric Acid journal October 2018
Comparative study of fluorinated single- and few-wall carbon nanotubes by X-ray photoelectron and X-ray absorption spectroscopy journal June 2009
Graphene Oxide as a Sulfur Immobilizer in High Performance Lithium/Sulfur Cells journal November 2011
Photoelectrochemical Processes at n-GaAs(100)/Aqueous HCl Electrolyte Interface: A Synchrotron Photoemission Spectroscopy Study of Emersed Electrodes journal June 2014
Chemisorbed Molecules under Potential Bias: Detailed Insights from First-Principles Vibrational Spectroscopies journal March 2014
Concentration and chemical-state profiles at heterogeneous interfaces with sub-nm accuracy from standing-wave ambient-pressure photoemission journal November 2014
Toward an Atomic-Scale Understanding of Electrochemical Interface Structure and Dynamics journal February 2019
The Coupling between Stability and Ion Pair Formation in Magnesium Electrolytes from First-Principles Quantum Mechanics and Classical Molecular Dynamics journal February 2015
Prediction of molecular properties and molecular spectroscopy with density functional theory: From fundamental theory to exchange-coupling journal March 2009
Prototype systems for rechargeable magnesium batteries journal October 2000
Role of Coordination Structure of Magnesium Ions on Charge and Discharge Behavior of Magnesium Alloy Electrode journal October 2018
Towards first principles modeling of electrochemical electrode–electrolyte interfaces journal January 2015
Polarized Near Edge X-ray Absorption Fine Structure Spectroscopic Study on Organized Molecular Films of Fluorinated Comb Polymers with Various Chain Lengths journal February 2002
Magnesium(II) Bis(trifluoromethane sulfonyl) Imide-Based Electrolytes with Wide Electrochemical Windows for Rechargeable Magnesium Batteries journal March 2014
Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries journal October 2004
Electrolytes and Interphases in Li-Ion Batteries and Beyond journal October 2014
Quest for Nonaqueous Multivalent Secondary Batteries: Magnesium and Beyond journal October 2014
Using “Tender” X-ray Ambient Pressure X-Ray Photoelectron Spectroscopy as A Direct Probe of Solid-Liquid Interface journal May 2015
A dynamic correlation dressed complete active space method: Theory, implementation, and preliminary applications journal December 2017
Towards a calcium-based rechargeable battery journal October 2015
Nanocomposite polymer electrolyte for rechargeable magnesium batteries journal March 2015
Electrolyte roadblocks to a magnesium rechargeable battery journal January 2012
Operating mechanisms of electrolytes in magnesium ion batteries: chemical equilibrium, magnesium deposition, and electrolyte oxidation journal January 2014

Similar Records

Electrolyte Reactivity on the MgV2O4 Cathode Surface
Journal Article · Sun Oct 08 00:00:00 EDT 2023 · ACS Applied Materials and Interfaces · OSTI ID:1838426
+12 more
Using soft x-ray absorption spectroscopy to characterize electrode/electrolyte interfaces in-situ and operando
Journal Article · Tue May 02 00:00:00 EDT 2017 · Journal of Electron Spectroscopy and Related Phenomena · OSTI ID:1838426
+3 more
Excitonic Effects in X-ray Absorption Spectra of Fluoride Salts and Their Surfaces
Journal Article · Tue Oct 11 00:00:00 EDT 2022 · Chemistry of Materials · OSTI ID:1838426
+5 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
In-situ/operando
Soft X-ray
XAS
Interface
Battery