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Title: Widening Electrochemical Window of Mg Salt by Weakly Coordinating Perfluoroalkoxyaluminate Anion for Mg Battery Electrolyte

Abstract

Energy storage concepts based on multivalent ion chemistries, such as Mg2+, promise very high volumetric energy density, however require improvements in electrolyte (Mg salt and solvent) electrochemical window to reach their full potential. Hypothetically the window of Mg salt could be widened by disfavoring the cathodic decomposition pathway of a thermodynamically and anodically stable anion, rendering it kinetically inert toward Mg+-mediated reduction. Computational and electrochemical analyses on Mg[TPFA](2) ([TPFA](-) = [Al{OC(CF3)(3)}(4)](-)) support this hypothesis, and showcase a widened electrochemical window as a result of mitigated cathodic decomposition as well as enhanced anodic stability from electron-withdrawing CF3 groups. Detailed NMR and IR spectroscopy and scanning electron microscopy/energy-dispersive X-ray spectroscopy further support that the weak coordination to Mg2+ in solution is important for maintaining the wide electrochemical window of Mg salt. (C) 2019 The Electrochemical Society.

Authors:
; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science - Office of Basic Energy Sciences - Joint Center for Energy Storage Research (JCESR)
OSTI Identifier:
1542632
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 166; Journal Issue: 8
Country of Publication:
United States
Language:
English
Subject:
Batteries, Energy storage, Battery, Electrolyte, Weakly coordinating anion

Citation Formats

Lau, Ka-Cheong, Seguin, Trevor, Carino, Emily V., Hahn, Nathan, Connell, Justin Grant, Ingram, Brian J., Ceder Persson, Kristin Aslaug, Zavadil, Kevin, and Liao, Chen. Widening Electrochemical Window of Mg Salt by Weakly Coordinating Perfluoroalkoxyaluminate Anion for Mg Battery Electrolyte. United States: N. p., 2019. Web. doi:10.1149/2.0751908jes.
Lau, Ka-Cheong, Seguin, Trevor, Carino, Emily V., Hahn, Nathan, Connell, Justin Grant, Ingram, Brian J., Ceder Persson, Kristin Aslaug, Zavadil, Kevin, & Liao, Chen. Widening Electrochemical Window of Mg Salt by Weakly Coordinating Perfluoroalkoxyaluminate Anion for Mg Battery Electrolyte. United States. doi:10.1149/2.0751908jes.
Lau, Ka-Cheong, Seguin, Trevor, Carino, Emily V., Hahn, Nathan, Connell, Justin Grant, Ingram, Brian J., Ceder Persson, Kristin Aslaug, Zavadil, Kevin, and Liao, Chen. Thu . "Widening Electrochemical Window of Mg Salt by Weakly Coordinating Perfluoroalkoxyaluminate Anion for Mg Battery Electrolyte". United States. doi:10.1149/2.0751908jes.
@article{osti_1542632,
title = {Widening Electrochemical Window of Mg Salt by Weakly Coordinating Perfluoroalkoxyaluminate Anion for Mg Battery Electrolyte},
author = {Lau, Ka-Cheong and Seguin, Trevor and Carino, Emily V. and Hahn, Nathan and Connell, Justin Grant and Ingram, Brian J. and Ceder Persson, Kristin Aslaug and Zavadil, Kevin and Liao, Chen},
abstractNote = {Energy storage concepts based on multivalent ion chemistries, such as Mg2+, promise very high volumetric energy density, however require improvements in electrolyte (Mg salt and solvent) electrochemical window to reach their full potential. Hypothetically the window of Mg salt could be widened by disfavoring the cathodic decomposition pathway of a thermodynamically and anodically stable anion, rendering it kinetically inert toward Mg+-mediated reduction. Computational and electrochemical analyses on Mg[TPFA](2) ([TPFA](-) = [Al{OC(CF3)(3)}(4)](-)) support this hypothesis, and showcase a widened electrochemical window as a result of mitigated cathodic decomposition as well as enhanced anodic stability from electron-withdrawing CF3 groups. Detailed NMR and IR spectroscopy and scanning electron microscopy/energy-dispersive X-ray spectroscopy further support that the weak coordination to Mg2+ in solution is important for maintaining the wide electrochemical window of Mg salt. (C) 2019 The Electrochemical Society.},
doi = {10.1149/2.0751908jes},
journal = {Journal of the Electrochemical Society},
number = 8,
volume = 166,
place = {United States},
year = {2019},
month = {5}
}

Works referenced in this record:

Li-ion battery materials: present and future
journal, June 2015


Mapping the Challenges of Magnesium Battery
journal, April 2016

  • Song, Jaehee; Sahadeo, Emily; Noked, Malachi
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 9
  • DOI: 10.1021/acs.jpclett.6b00384

Odyssey of Multivalent Cathode Materials: Open Questions and Future Challenges
journal, February 2017

  • Canepa, Pieremanuele; Sai Gautam, Gopalakrishnan; Hannah, Daniel C.
  • Chemical Reviews, Vol. 117, Issue 5
  • DOI: 10.1021/acs.chemrev.6b00614

Electrolyte roadblocks to a magnesium rechargeable battery
journal, January 2012

  • Muldoon, John; Bucur, Claudiu B.; Oliver, Allen G.
  • Energy & Environmental Science, Vol. 5, Issue 3, p. 5941-5950
  • DOI: 10.1039/c2ee03029b

Mg rechargeable batteries: an on-going challenge
journal, January 2013

  • Yoo, Hyun Deog; Shterenberg, Ivgeni; Gofer, Yosef
  • Energy & Environmental Science, Vol. 6, Issue 8, p. 2265-2279
  • DOI: 10.1039/c3ee40871j

Fervent Hype behind Magnesium Batteries: An Open Call to Synthetic Chemists-Electrolytes and Cathodes Needed
journal, August 2017

  • Muldoon, John; Bucur, Claudiu B.; Gregory, Thomas
  • Angewandte Chemie International Edition, Vol. 56, Issue 40
  • DOI: 10.1002/anie.201700673

Spinel compounds as multivalent battery cathodes: a systematic evaluation based on ab initio calculations
journal, January 2015

  • Liu, Miao; Rong, Ziqin; Malik, Rahul
  • Energy & Environmental Science, Vol. 8, Issue 3
  • DOI: 10.1039/C4EE03389B

Corrosion of magnesium electrolytes: chlorides – the culprit
journal, December 2012

  • Muldoon, John; Bucur, Claudiu B.; Oliver, Allen G.
  • Energy Environ. Sci., Vol. 6, Issue 2, p. 482-487
  • DOI: 10.1039/C2EE23686A

Magnesium Borohydride: From Hydrogen Storage to Magnesium Battery
journal, August 2012

  • Mohtadi, Rana; Matsui, Masaki; Arthur, Timothy S.
  • Angewandte Chemie International Edition, Vol. 51, Issue 39, p. 9780-9783
  • DOI: 10.1002/anie.201204913

Prototype systems for rechargeable magnesium batteries
journal, October 2000

  • Aurbach, D.; Lu, Z.; Schechter, A.
  • Nature, Vol. 407, Issue 6805, p. 724-727
  • DOI: 10.1038/35037553

Structural Analysis of Electrolyte Solutions Comprising Magnesium−Aluminate Chloro−Organic Complexes by Raman Spectroscopy
journal, June 2007

  • Vestfried, Yulia; Chusid, Orit; Goffer, Yossi
  • Organometallics, Vol. 26, Issue 13
  • DOI: 10.1021/om061076s

Structural Analysis of Electrolyte Solutions for Rechargeable Mg Batteries by Stereoscopic Means and DFT Calculations
journal, April 2011

  • Pour, Nir; Gofer, Yossi; Major, Dan T.
  • Journal of the American Chemical Society, Vol. 133, Issue 16
  • DOI: 10.1021/ja1098512

Novel, electrolyte solutions comprising fully inorganic salts with high anodic stability for rechargeable magnesium batteries
journal, January 2014

  • Doe, Robert E.; Han, Ruoban; Hwang, Jaehee
  • Chemical Communications, Vol. 50, Issue 2, p. 243-245
  • DOI: 10.1039/C3CC47896C

A facile approach using MgCl2 to formulate high performance Mg2+ electrolytes for rechargeable Mg batteries
journal, January 2014

  • Liu, Tianbiao; Shao, Yuyan; Li, Guosheng
  • Journal of Materials Chemistry A, Vol. 2, Issue 10
  • DOI: 10.1039/c3ta14825d

Structure and compatibility of a magnesium electrolyte with a sulphur cathode
journal, August 2011

  • Kim, Hee Soo; Arthur, Timothy S.; Allred, Gary D.
  • Nature Communications, Vol. 2, Article No. 427
  • DOI: 10.1038/ncomms1435

The unexpected discovery of the Mg(HMDS) 2 /MgCl 2 complex as a magnesium electrolyte for rechargeable magnesium batteries
journal, January 2015

  • Liao, Chen; Sa, Niya; Key, Baris
  • Journal of Materials Chemistry A, Vol. 3, Issue 11
  • DOI: 10.1039/C5TA00118H

Practical Stability Limits of Magnesium Electrolytes
journal, January 2016

  • Lipson, Albert L.; Han, Sang-Don; Pan, Baofei
  • Journal of The Electrochemical Society, Vol. 163, Issue 10
  • DOI: 10.1149/2.0451610jes

A new class of non-corrosive, highly efficient electrolytes for rechargeable magnesium batteries
journal, January 2017

  • Zhao-Karger, Zhirong; Gil Bardaji, Maria Elisa; Fuhr, Olaf
  • Journal of Materials Chemistry A, Vol. 5, Issue 22
  • DOI: 10.1039/C7TA02237A

A Fluorinated Alkoxyaluminate Electrolyte for Magnesium-Ion Batteries
journal, November 2016


An Efficient Halogen-Free Electrolyte for Use in Rechargeable Magnesium Batteries
journal, May 2015

  • Tutusaus, Oscar; Mohtadi, Rana; Arthur, Timothy S.
  • Angewandte Chemie International Edition, Vol. 54, Issue 27
  • DOI: 10.1002/anie.201412202

Cation reduction and comproportionation as novel strategies to produce high voltage, halide free, carborane based electrolytes for rechargeable Mg batteries
journal, January 2015

  • McArthur, Scott. G.; Geng, Linxiao; Guo, Juchen
  • Inorganic Chemistry Frontiers, Vol. 2, Issue 12
  • DOI: 10.1039/C5QI00171D

Enhanced Stability of the Carba- closo -dodecaborate Anion for High-Voltage Battery Electrolytes through Rational Design
journal, July 2018

  • Hahn, Nathan T.; Seguin, Trevor J.; Lau, Ka-Cheong
  • Journal of the American Chemical Society, Vol. 140, Issue 35
  • DOI: 10.1021/jacs.8b05967

Electrochemical Properties of Quaternary Ammonium Salts for Electrochemical Capacitors
journal, January 1997

  • Ue, Makoto
  • Journal of The Electrochemical Society, Vol. 144, Issue 8
  • DOI: 10.1149/1.1837882

On the electrochemical behavior of magnesium electrodes in polar aprotic electrolyte solutions
journal, May 1999


Mg(PF 6 ) 2 -Based Electrolyte Systems: Understanding Electrolyte–Electrode Interactions for the Development of Mg-Ion Batteries
journal, July 2016

  • Keyzer, Evan N.; Glass, Hugh F. J.; Liu, Zigeng
  • Journal of the American Chemical Society, Vol. 138, Issue 28
  • DOI: 10.1021/jacs.6b04319

Hexafluorophosphate-Based Solutions for Mg Batteries and the Importance of Chlorides
journal, July 2017


The Coupling between Stability and Ion Pair Formation in Magnesium Electrolytes from First-Principles Quantum Mechanics and Classical Molecular Dynamics
journal, February 2015

  • Rajput, Nav Nidhi; Qu, Xiaohui; Sa, Niya
  • Journal of the American Chemical Society, Vol. 137, Issue 9, p. 3411-3420
  • DOI: 10.1021/jacs.5b01004

Carboranes:  A New Class of Weakly Coordinating Anions for Strong Electrophiles, Oxidants, and Superacids
journal, March 1998

  • Reed, Christopher A.
  • Accounts of Chemical Research, Vol. 31, Issue 3
  • DOI: 10.1021/ar970230r

Noncoordinating Anions—Fact or Fiction? A Survey of Likely Candidates
journal, April 2004

  • Krossing, Ingo; Raabe, Ines
  • Angewandte Chemie International Edition, Vol. 43, Issue 16
  • DOI: 10.1002/anie.200300620

Development of Catalysts and Ligands for Enantioselective Gold Catalysis
journal, November 2013

  • Wang, Yi-Ming; Lackner, Aaron D.; Toste, F. Dean
  • Accounts of Chemical Research, Vol. 47, Issue 3
  • DOI: 10.1021/ar400188g

A New Approach to Non-Coordinating Anions: Lewis Acid Enhancement of Porphyrin Metal Centers in a Zwitterionic Metal–Organic Framework
journal, August 2016

  • Johnson, Jacob A.; Petersen, Brenna M.; Kormos, Attila
  • Journal of the American Chemical Society, Vol. 138, Issue 32
  • DOI: 10.1021/jacs.6b05626

Advances in Non-Metallocene Olefin Polymerization Catalysis
journal, January 2003

  • Gibson, Vernon C.; Spitzmesser, Stefan K.
  • Chemical Reviews, Vol. 103, Issue 1
  • DOI: 10.1021/cr980461r

A Fusible Orthoborate Lithium Salt with High Conductivity in Solutions
journal, January 1999

  • Xu, Wu
  • Electrochemical and Solid-State Letters, Vol. 3, Issue 8
  • DOI: 10.1149/1.1391150

Ionic Liquids with Weakly Coordinating [M III (OR F ) 4 ] Anions
journal, August 2015


B(SCN) 4 : A New Weakly Coordinating Anion in the Tetracyanoborate Family
journal, December 2017

  • Zhong, Mingmin; Fang, Hong; Jena, Puru
  • The Journal of Physical Chemistry C, Vol. 122, Issue 25
  • DOI: 10.1021/acs.jpcc.7b10332

Mg Desolvation and Intercalation Mechanism at the Mo 6 S 8 Chevrel Phase Surface
journal, August 2015


A Stable, Non-Corrosive Perfluorinated Pinacolatoborate Mg Electrolyte for Rechargeable Mg Batteries
journal, March 2019

  • Luo, Jian; Bi, Yujing; Zhang, Liping
  • Angewandte Chemie International Edition, Vol. 58, Issue 21
  • DOI: 10.1002/anie.201902009

Fluorinated Alkoxide-Based Magnesium-Ion Battery Electrolytes that Demonstrate Li-Ion-Battery-Like High Anodic Stability and Solution Conductivity
journal, August 2016

  • Crowe, Adam J.; Stringham, Kyle K.; Bartlett, Bart M.
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 35
  • DOI: 10.1021/acsami.6b07262

A general synthetic methodology to access magnesium aluminate electrolyte systems for Mg batteries
journal, January 2019

  • Keyzer, Evan N.; Lee, Jeongjae; Liu, Zigeng
  • Journal of Materials Chemistry A, Vol. 7, Issue 6
  • DOI: 10.1039/C8TA10295C

A nuclear magnetic resonance spectroscopic technique for the characterization of lithium ion pair structures in THF and THF/HMPA solution
journal, September 1993

  • Reich, Hans J.; Borst, Joseph P.; Dykstra, Robert R.
  • Journal of the American Chemical Society, Vol. 115, Issue 19
  • DOI: 10.1021/ja00072a028

Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries
journal, October 2004


Early Stage Anodic Instability of Glassy Carbon Electrodes in Propylene Carbonate Solvent Containing Lithium Hexafluorophosphate
journal, August 2017


Study of Electrochemical Phenomena Observed at the Mg Metal/Electrolyte Interface
journal, December 2016


On the Mechanisms of Reversible Magnesium Deposition Processes
journal, January 2001

  • Aurbach, Doron; Schechter, Alexander; Moshkovich, Moty
  • Journal of The Electrochemical Society, Vol. 148, Issue 9
  • DOI: 10.1149/1.1387980

Study on electrochemically deposited Mg metal
journal, August 2011


Chemistry with weakly-coordinating fluorinated alkoxyaluminate anions: Gas phase cations in condensed phases?
journal, November 2006


Tetraalkylammonium Salts of Weakly Coordinating Aluminates: Ionic Liquids, Materials for Electrochemical Applications and Useful Compounds for Anion Investigation
journal, February 2009

  • Raabe, Ines; Wagner, Katrin; Guttsche, Kristin
  • Chemistry - A European Journal, Vol. 15, Issue 8
  • DOI: 10.1002/chem.200800417

The Electrolyte Genome project: A big data approach in battery materials discovery
journal, June 2015


Systematic optimization of long-range corrected hybrid density functionals
journal, February 2008

  • Chai, Jeng-Da; Head-Gordon, Martin
  • The Journal of Chemical Physics, Vol. 128, Issue 8
  • DOI: 10.1063/1.2834918

Quantum Mechanical Continuum Solvation Models
journal, August 2005

  • Tomasi, Jacopo; Mennucci, Benedetta; Cammi, Roberto
  • Chemical Reviews, Vol. 105, Issue 8
  • DOI: 10.1021/cr9904009