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Title: Allotropic control: How certain fluorinated carbonate electrolytes protect aluminum current collectors by promoting the formation of insoluble coordination polymers

Abstract

Here, there is a strong incentive for increasing the operation voltage of Li-ion cells above 4.5 V in order to increase the density of stored energy. Aluminum is an inexpensive, lightweight metal that is commonly used as a positive electrode current collector in these cells. Imide LiX salts, such as lithium bis(trifluoromethylsulfonyl)imide (X = TFSI), and lithium bis(fluorosulfonyl)imide (X = FSI), are chemically stable on the energized lithiated transition metal oxide electrodes, but their presence in the electrolyte causes rapid anodic dissolution and pitting of Al current collectors at potentials exceeding 4.0 V versus Li/Li+. For LiBF4 and LiPF6, the release of HF near the energized surfaces passivates the exposed Al metal, inhibiting this pitting corrosion, but it also causes the gradual degradation of the cathode active material, negating this important advantage. Here we report that in certain electrolytes containing fluorinated carbonate solvents and LiX salts, the threshold voltage for safe operation of Al current collectors can be increased to 5.5 V versus Li/Li+. Interestingly, the most efficient solvent also facilitates the formation of an insoluble gel when AlX3 is introduced into this solvent. We suggest that this solvent promotes the aggregation of coordination polymers of AlX3 at the exposedmore » Al surface that isolate this surface from the electrolyte, thereby preventing further Al dissolution and corrosion. Other examples of Al collector protection may also involve this mechanism. Our study suggests that such “allotropic control” could be a way of widening the operation window of Li-ion cells without electrode deterioration, Al current collector corrosion, and electrolyte breakdown.« less

Authors:
 [1];  [1];  [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1337952
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 120; Journal Issue: 33; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; aluminum collector corrosion; coordination polymer; electrolyte; lithium ion batteries

Citation Formats

Shkrob, Ilya A., Pupek, Krzysztof Z., and Abraham, Daniel P.. Allotropic control: How certain fluorinated carbonate electrolytes protect aluminum current collectors by promoting the formation of insoluble coordination polymers. United States: N. p., 2016. Web. https://doi.org/10.1021/acs.jpcc.6b05241.
Shkrob, Ilya A., Pupek, Krzysztof Z., & Abraham, Daniel P.. Allotropic control: How certain fluorinated carbonate electrolytes protect aluminum current collectors by promoting the formation of insoluble coordination polymers. United States. https://doi.org/10.1021/acs.jpcc.6b05241
Shkrob, Ilya A., Pupek, Krzysztof Z., and Abraham, Daniel P.. Thu . "Allotropic control: How certain fluorinated carbonate electrolytes protect aluminum current collectors by promoting the formation of insoluble coordination polymers". United States. https://doi.org/10.1021/acs.jpcc.6b05241. https://www.osti.gov/servlets/purl/1337952.
@article{osti_1337952,
title = {Allotropic control: How certain fluorinated carbonate electrolytes protect aluminum current collectors by promoting the formation of insoluble coordination polymers},
author = {Shkrob, Ilya A. and Pupek, Krzysztof Z. and Abraham, Daniel P.},
abstractNote = {Here, there is a strong incentive for increasing the operation voltage of Li-ion cells above 4.5 V in order to increase the density of stored energy. Aluminum is an inexpensive, lightweight metal that is commonly used as a positive electrode current collector in these cells. Imide LiX salts, such as lithium bis(trifluoromethylsulfonyl)imide (X = TFSI), and lithium bis(fluorosulfonyl)imide (X = FSI), are chemically stable on the energized lithiated transition metal oxide electrodes, but their presence in the electrolyte causes rapid anodic dissolution and pitting of Al current collectors at potentials exceeding 4.0 V versus Li/Li+. For LiBF4 and LiPF6, the release of HF near the energized surfaces passivates the exposed Al metal, inhibiting this pitting corrosion, but it also causes the gradual degradation of the cathode active material, negating this important advantage. Here we report that in certain electrolytes containing fluorinated carbonate solvents and LiX salts, the threshold voltage for safe operation of Al current collectors can be increased to 5.5 V versus Li/Li+. Interestingly, the most efficient solvent also facilitates the formation of an insoluble gel when AlX3 is introduced into this solvent. We suggest that this solvent promotes the aggregation of coordination polymers of AlX3 at the exposed Al surface that isolate this surface from the electrolyte, thereby preventing further Al dissolution and corrosion. Other examples of Al collector protection may also involve this mechanism. Our study suggests that such “allotropic control” could be a way of widening the operation window of Li-ion cells without electrode deterioration, Al current collector corrosion, and electrolyte breakdown.},
doi = {10.1021/acs.jpcc.6b05241},
journal = {Journal of Physical Chemistry. C},
number = 33,
volume = 120,
place = {United States},
year = {2016},
month = {7}
}

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Works referenced in this record:

Fluorinated Electrolytes for 5-V Li-Ion Chemistry: Synthesis and Evaluation of an Additive for High-Voltage LiNi 0.5 Mn 1.5 O 4 /Graphite Cell
journal, January 2014

  • Hu, Libo; Xue, Zheng; Amine, Khalil
  • Journal of The Electrochemical Society, Vol. 161, Issue 12
  • DOI: 10.1149/2.0141412jes

Fluorinated electrolytes for 5 V lithium-ion battery chemistry
journal, January 2013

  • Zhang, Zhengcheng; Hu, Libo; Wu, Huiming
  • Energy & Environmental Science, Vol. 6, Issue 6
  • DOI: 10.1039/c3ee24414h

Current Collectors for Positive Electrodes of Lithium-Based Batteries
journal, January 2005

  • Whitehead, Adam H.; Schreiber, Martha
  • Journal of The Electrochemical Society, Vol. 152, Issue 11
  • DOI: 10.1149/1.2039587

Aluminum Corrosion in Lithium Batteries An Investigation Using the Electrochemical Quartz Crystal Microbalance
journal, January 2000

  • Yang, Haesik; Kwon, Kyungjung; Devine, Thomas M.
  • Journal of The Electrochemical Society, Vol. 147, Issue 12
  • DOI: 10.1149/1.1394077

Surface reconstruction and chemical evolution of stoichiometric layered cathode materials for lithium-ion batteries
journal, March 2014

  • Lin, Feng; Markus, Isaac M.; Nordlund, Dennis
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms4529

On the Electrochemical Behavior of Aluminum Electrodes in Nonaqueous Electrolyte Solutions of Lithium Salts
journal, January 2010

  • Markovsky, Boris; Amalraj, Francis; Gottlieb, Hugo E.
  • Journal of The Electrochemical Society, Vol. 157, Issue 4
  • DOI: 10.1149/1.3294774

Corrosion of Aluminum Current Collectors in High-Power Lithium-Ion Batteries for Use in Hybrid Electric Vehicles
journal, January 2007

  • Hyams, Tzipi Cohen; Go, John; Devine, Thomas M.
  • Journal of The Electrochemical Society, Vol. 154, Issue 8
  • DOI: 10.1149/1.2742321

Electrochemical behavior and passivation of current collectors in lithium-ion batteries
journal, January 2011

  • Myung, Seung-Taek; Hitoshi, Yashiro; Sun, Yang-Kook
  • Journal of Materials Chemistry, Vol. 21, Issue 27
  • DOI: 10.1039/c0jm04353b

Transport and Electrochemical Properties and Spectral Features of Non-Aqueous Electrolytes Containing LiFSI in Linear Carbonate Solvents
journal, January 2011

  • Li, Lifei; Zhou, Sisi; Han, Hongbo
  • Journal of The Electrochemical Society, Vol. 158, Issue 2
  • DOI: 10.1149/1.3514705

Corrosion/passivation of aluminum current collector in bis(fluorosulfonyl)imide-based ionic liquid for lithium-ion batteries
journal, August 2012


Anodic behavior of aluminum in organic solutions with different electrolytic salts for lithium ion batteries
journal, July 2002


Aluminum corrosion in electrolyte of Li-ion battery
journal, July 2002


Characteristics of the electrolyte with fluoro organic lithium salts
journal, September 2000


Suppression of Aluminum Corrosion in Lithium Bis(trifluoromethanesulfonyl)imide-based Electrolytes by the Addition of Fumed Silica
journal, June 2013

  • Louis, Hamenu; Lee, Young-Gi; Kim, Kwang Man
  • Bulletin of the Korean Chemical Society, Vol. 34, Issue 6
  • DOI: 10.5012/bkcs.2013.34.6.1795

Mechanism of Anodic Dissolution of the Aluminum Current Collector in 1 M LiTFSI EC:DEC 3:7 in Rechargeable Lithium Batteries
journal, December 2012

  • Krämer, Elisabeth; Schedlbauer, Tanja; Hoffmann, Björn
  • Journal of The Electrochemical Society, Vol. 160, Issue 2
  • DOI: 10.1149/2.081302jes

EMIIm and EMIBeti on Aluminum Anodic Stability Dependence on Lithium Salt and Propylene Carbonate
journal, January 1999

  • Goldman, Jay L.
  • Electrochemical and Solid-State Letters, Vol. 2, Issue 10
  • DOI: 10.1149/1.1390883

Suppression of aluminum current collector corrosion in ionic liquid containing electrolytes
journal, September 2012


Anodic behavior of Al current collector in 1-alkyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl] amide ionic liquid electrolytes
journal, November 2007


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


Mechanism of hydrofluoric acid formation in ethylene carbonate electrolytes with fluorine salt additives
journal, November 2015


An Experimental and Theoretical Study of the Aluminium Species Present in Mixtures of AlCl 3 with the Ionic Liquids [BMP]Tf 2 N and [EMIm]Tf 2 N
journal, March 2009

  • Eiden, Philipp; Liu, Qunxian; Zein El Abedin, Sherif
  • Chemistry - A European Journal, Vol. 15, Issue 14
  • DOI: 10.1002/chem.200801616

Aluminium Speciation in 1-Butyl-1-Methylpyrrolidinium Bis(trifluoromethylsulfonyl)amide/AlCl 3 Mixtures
journal, March 2009

  • Rocher, Nathalie M.; Izgorodina, Ekaterina I.; Rüther, Thomas
  • Chemistry - A European Journal, Vol. 15, Issue 14
  • DOI: 10.1002/chem.200801641

Fluorinated Electrolytes for 5-V Li-Ion Chemistry: Probing Voltage Stability of Electrolytes with Electrochemical Floating Test
journal, January 2015

  • He, Meinan; Hu, Libo; Xue, Zheng
  • Journal of The Electrochemical Society, Vol. 162, Issue 9
  • DOI: 10.1149/2.0231509jes

Perfluoroalkyl-substituted ethylene carbonates: Novel electrolyte additives for high-voltage lithium-ion batteries
journal, January 2014


Spontaneous aggregation of lithium ion coordination polymers in fluorinated electrolytes for high-voltage batteries
journal, January 2016

  • Malliakas, Christos D.; Leung, Kevin; Pupek, Krzysztof Z.
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 16
  • DOI: 10.1039/C6CP01157H

On the performance of the semiempirical quantum mechanical PM6 and PM7 methods for noncovalent interactions
journal, May 2013


GPU Linear Algebra Libraries and GPGPU Programming for Accelerating MOPAC Semiempirical Quantum Chemistry Calculations
journal, August 2012

  • Maia, Julio Daniel Carvalho; Urquiza Carvalho, Gabriel Aires; Mangueira, Carlos Peixoto
  • Journal of Chemical Theory and Computation, Vol. 8, Issue 9
  • DOI: 10.1021/ct3004645

Suppression of aluminum corrosion by using high concentration LiTFSI electrolyte
journal, June 2013


Concentrated electrolytes: decrypting electrolyte properties and reassessing Al corrosion mechanisms
journal, January 2014

  • McOwen, Dennis W.; Seo, Daniel M.; Borodin, Oleg
  • Energy Environ. Sci., Vol. 7, Issue 1
  • DOI: 10.1039/C3EE42351D

Friedel-Crafts chemistry. 11. Boron, aluminum, and gallium tris(trifluoromethanesulfonate) (triflate): effective new Friedel-Crafts catalysts
journal, April 1988

  • Olah, George A.; Farooq, Omar.; Farnia, S. M. F.
  • Journal of the American Chemical Society, Vol. 110, Issue 8
  • DOI: 10.1021/ja00216a032

Aluminium triflate: a remarkable Lewis acid catalyst for the ring opening of epoxides by alcohols
journal, January 2005

  • Williams, D. Bradley G.; Lawton, Michelle
  • Organic & Biomolecular Chemistry, Vol. 3, Issue 18
  • DOI: 10.1039/b508924g

Metal Triflimidates: Better than Metal Triflates as Catalysts in Organic Synthesis-The Effect of a Highly Delocalized Counteranion
journal, August 2010

  • Antoniotti, Sylvain; Dalla, Vincent; Duñach, Elisabet
  • Angewandte Chemie International Edition, Vol. 49, Issue 43, p. 7860-7888
  • DOI: 10.1002/anie.200906407

Dissolution of Metal Salts in Bis(trifluoromethylsulfonyl)imide-Based Ionic Liquids: Studying the Affinity of Metal Cations Toward a “Weakly Coordinating” Anion
journal, November 2014

  • Bortolini, Olga; Chiappe, Cinzia; Ghilardi, Tiziana
  • The Journal of Physical Chemistry A, Vol. 119, Issue 21
  • DOI: 10.1021/jp507437g

In the Bottlebrush Garden: The Structural Aspects of Coordination Polymer Phases formed in Lanthanide Extraction with Alkyl Phosphoric Acids
journal, August 2015

  • Ellis, Ross J.; Demars, Thomas; Liu, Guokui
  • The Journal of Physical Chemistry B, Vol. 119, Issue 35
  • DOI: 10.1021/acs.jpcb.5b05679

    Works referencing / citing this record:

    Transition Metal Dissolution, Ion Migration, Electrocatalytic Reduction and Capacity Loss in Lithium-Ion Full Cells
    journal, December 2016

    • Gilbert, James A.; Shkrob, Ilya A.; Abraham, Daniel P.
    • Journal of The Electrochemical Society, Vol. 164, Issue 2
    • DOI: 10.1149/2.1111702jes

    Understanding and development of olivine LiCoPO 4 cathode materials for lithium-ion batteries
    journal, January 2018

    • Zhang, Min; Garcia-Araez, Nuria; Hector, Andrew L.
    • Journal of Materials Chemistry A, Vol. 6, Issue 30
    • DOI: 10.1039/c8ta04063j

    Structures and dynamic properties of the LiPF 6 electrolytic solution under electric fields – a theoretical study
    journal, January 2019

    • Liu, Man; Chimtali, Peter J.; Huang, Xue-bin
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 24
    • DOI: 10.1039/c9cp00561g

    Hybrid electrolyte enables safe and practical 5 V LiNi 0.5 Mn 1.5 O 4 batteries
    journal, January 2019

    • Chandra Rath, Purna; Wu, Chia-Jung; Patra, Jagabandhu
    • Journal of Materials Chemistry A, Vol. 7, Issue 27
    • DOI: 10.1039/c9ta04147h