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Instability at the Electrode/Electrolyte Interface Induced by Hard Cation Chelation and Nucleophilic Attack

Journal Article · · Chemistry of Materials
 [1];  [2];  [2];  [3];  [4];  [3];  [2];  [2];  [2]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of Maryland, College Park, MD (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  3. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Chinese Academy of Sciences (CAS), Shanghai (China)
+ Show Author Affiliations
Electrochemistry is necessarily a science of interfacial processes, and understanding electrode/electrolyte interfaces is essential to controlling electrochemical performance and stability. Undesirable interfacial interactions hinder discovery and development of rational materials combinations. By example, we examine an electrolyte, magnesium(II) bis(trifluoromethanesulfonyl)imide (Mg(TFSI)2) dissolved in diglyme, next to the Mg metal anode, which is purported to have a wide window of electrochemical stability. However, even in the absence of any bias, using in situ tender X-ray photoelectron spectroscopy, we discovered an intrinsic interfacial chemical instability of both the solvent and salt, further explained using first-principles calculations as driven by Mg2+ dication chelation and nucleophilic attack by hydroxide ions. The proposed mechanism appears general to the chemistry near or on metal surfaces in hygroscopic environments with chelation of hard cations and indicates possible synthetic strategies to overcome chemical instability within this class of electrolytes.
Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Nanostructures for Electrical Energy Storage (NEES); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center; Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC02-05CH11231; AC04-94AL85000; SC0001160
OSTI ID:
1473937
Alternate ID(s):
OSTI ID: 1480074
Report Number(s):
SAND--2018-9890J; 667716
Journal Information:
Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 19 Vol. 29; ISSN 0897-4756
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

References (62)

Density-functional method for very large systems with LCAO basis sets journal January 1997
Transition-Metal-Free Magnesium-Based Batteries Activated by Anionic Insertion into Fluorinated Graphene Nanosheets journal September 2015
Robust Cycling of Li-O 2 Batteries through the Synergistic Effect of Blended Electrolytes journal February 2013
XPS O 1s binding energies for polymers containing hydroxyl, ether, ketone and ester groups journal May 1991
Q-Chem: an engine for innovation: Q-Chem: an engine for innovation journal November 2012
cp2k: atomistic simulations of condensed matter systems
  • Hutter, Jürg; Iannuzzi, Marcella; Schiffmann, Florian
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 4, Issue 1 https://doi.org/10.1002/wcms.1159
journal June 2013
Studies of the charging of insulators in ESCA journal January 1980
Relaxation energies in XPS and XAES of solid sulfur compounds journal May 1994
Magnesium insertion electrodes for rechargeable nonaqueous batteries — a competitive alternative to lithium? journal September 1999
Electrochemical reduction of an anion for ionic-liquid molecules on a lithium electrode studied by first-principles calculations journal September 2014
Electrodeposited Bi, Sb and Bi1-xSbx alloys as anodes for Mg-ion batteries journal March 2012
Is alpha-V2O5 a cathode material for Mg insertion batteries? journal August 2016
XPS studies of the oxygen 1s and 2s levels in a wide range of functional polymers journal June 1993
Understanding the Initial Stages of Reversible Mg Deposition and Stripping in Inorganic Nonaqueous Electrolytes journal April 2015
Tuning the Reversibility of Mg Anodes via Controlled Surface Passivation by H 2 O/Cl – in Organic Electrolytes journal October 2016
A Combined Experimental and Computational Study of an Aluminum Triflate/Diglyme Electrolyte journal September 2015
Solvation of Magnesium Ion in Triglyme-Based Electrolyte Solutions journal August 2015
Reactivity at the Lithium–Metal Anode Surface of Lithium–Sulfur Batteries journal November 2015
Exploration of the Detailed Conditions for Reductive Stability of Mg(TFSI) 2 in Diglyme: Implications for Multivalent Electrolytes journal February 2016
Electrochemical Stability of Magnesium Surfaces in an Aqueous Environment journal November 2016
Interface-Induced Renormalization of Electrolyte Energy Levels in Magnesium Batteries journal February 2016
Study of Electrochemical Phenomena Observed at the Mg Metal/Electrolyte Interface journal December 2016
Magnesium(II) Bis(trifluoromethane sulfonyl) Imide-Based Electrolytes with Wide Electrochemical Windows for Rechargeable Magnesium Batteries journal March 2014
Electrochemical Windows of Room-Temperature Ionic Liquids from Molecular Dynamics and Density Functional Theory Calculations journal June 2011
Thermodynamic Oxidation and Reduction Potentials of Photocatalytic Semiconductors in Aqueous Solution journal September 2012
Quantum Chemistry on Graphical Processing Units. 3. Analytical Energy Gradients, Geometry Optimization, and First Principles Molecular Dynamics journal August 2009
van der Waals Volumes and Radii journal March 1964
UFF, a full periodic table force field for molecular mechanics and molecular dynamics simulations journal December 1992
Theoretical Studies To Understand Surface Chemistry on Carbon Anodes for Lithium-Ion Batteries:  Reduction Mechanisms of Ethylene Carbonate journal November 2001
The Coupling between Stability and Ion Pair Formation in Magnesium Electrolytes from First-Principles Quantum Mechanics and Classical Molecular Dynamics journal February 2015
Dissociation of Water on MgO(100) journal February 2002
XPS Valence Characterization of Lithium Salts as a Tool to Study Electrode/Electrolyte Interfaces of Li-Ion Batteries journal July 2006
Mechanism of Heterogeneous Reaction of Carbonyl Sulfide on Magnesium Oxide journal April 2007
Structures of the Ordered Water Monolayer on MgO(001) journal March 2011
Sacrificial Anion Reduction Mechanism for Electrochemical Stability Improvement in Highly Concentrated Li-Salt Electrolyte journal June 2014
DL-FIND: An Open-Source Geometry Optimizer for Atomistic Simulations † journal October 2009
Dissociation of Water at the MgO(100)−Water Interface:  Comparison of Theory with Experiment journal April 1999
Mechanisms of water interaction with a magnesium oxide surface journal July 1985
XPS Investigation of Surface Chemistry of Magnesium Electrodes in Contact with Organic Solutions of Organochloroaluminate Complex Salts journal March 2003
Surface Reduction of Poly(aryl ether ether ketone) Film:  UV Spectrophotometric, 3H Radiochemical, and X-ray Photoelectron Spectroscopic Assays of the Hydroxyl Functions journal February 1997
Dynamic formation of a solid-liquid electrolyte interphase and its consequences for hybrid-battery concepts journal March 2016
Unravelling the electrochemical double layer by direct probing of the solid/liquid interface journal August 2016
Using “Tender” X-ray Ambient Pressure X-Ray Photoelectron Spectroscopy as A Direct Probe of Solid-Liquid Interface journal May 2015
Surface characterization and stability phenomena in Li 2 FeSiO 4 studied by PES/XPS journal January 2006
A comparative XPS surface study of Li 2 FeSiO 4 /C cycled with LiTFSI- and LiPF 6 -based electrolytes journal January 2009
Operating mechanisms of electrolytes in magnesium ion batteries: chemical equilibrium, magnesium deposition, and electrolyte oxidation journal January 2014
Solvation structure and energetics of electrolytes for multivalent energy storage journal January 2014
Interface layer formation in solid polymer electrolyte lithium batteries: an XPS study journal January 2014
Interaction of the ionic liquid [BMP][TFSA] with rutile TiO 2 (110) and coadsorbed lithium journal January 2016
Direct observation of the energetics at a semiconductor/liquid junction by operando X-ray photoelectron spectroscopy journal January 2015
COSMO: a new approach to dielectric screening in solvents with explicit expressions for the screening energy and its gradient journal January 1993
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu journal April 2010
First-principles calculations of charged surfaces and interfaces: A plane-wave nonrepeated slab approach journal March 2006
Partial Dissociation of Water Molecules in the ( 3 × 2 ) Water Monolayer Deposited on the MgO (100) Surface journal August 1998
Empirical bond-strength–bond-length curves for oxides journal May 1973
Review—Development of Advanced Rechargeable Batteries: A Continuous Challenge in the Choice of Suitable Electrolyte Solutions journal January 2015
Evaluation of Mg[N(SO 2 CF 3 ) 2 ] 2 /Acetonitrile Electrolyte for Use in Mg-Ion Cells journal January 2012
Evaluation of (CF 3 SO 2 ) 2 N − (TFSI) Based Electrolyte Solutions for Mg Batteries journal January 2015
LiTFSI Stability in Water and Its Possible Use in Aqueous Lithium-Ion Batteries: pH Dependency, Electrochemical Window and Temperature Stability journal January 2013
XPS Binding Energies of Deep Core Levels and the Auger Parameter - An Application to Solid Sulfur Compounds journal June 1993
Electrochemistry at Negative Potentials in Bis(trifluoromethanesulfonyl)amide Ionic Liquids journal October 2006
Magnesium batteries: Current state of the art, issues and future perspectives journal January 2014

Cited By (5)

Probing a battery electrolyte drop with ambient pressure photoelectron spectroscopy text January 2019
Rechargeable Magnesium–Sulfur Battery Technology: State of the Art and Key Challenges journal September 2019
Rechargeable Magnesium Batteries using Conversion-Type Cathodes: A Perspective and Minireview journal July 2018
Probing a battery electrolyte drop with ambient pressure photoelectron spectroscopy journal July 2019
Dendrite Growth in Mg Metal Cells Containing Mg(TFSI) 2 /Glyme Electrolytes journal January 2018

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