Chemical stability of Lithium 2-trifluoromethyl-4,5-dicyanoimidazolide, an electrolyte salt for Li-ion cells

Shkrob, Ilya A.; Pupek, Krzysztof Z.; Gilbert, James A.; Trask, Stephen E.; Abraham, Daniel P.

doi:10.1021/acs.jpcc.6b09837

Title: Chemical stability of Lithium 2-trifluoromethyl-4,5-dicyanoimidazolide, an electrolyte salt for Li-ion cells

Journal Article · Thu Dec 01 00:00:00 EST 2016 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.6b09837· OSTI ID:1337946

^[1]; Pupek, Krzysztof Z. ^[2]; Gilbert, James A. ^[1]; Trask, Stephen E. ^[1]; Abraham, Daniel P. ^[1]

Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
Argonne National Lab. (ANL), Argonne, IL (United States). Materials Engineering Research Facility

Lithium hexafluorophosphate (LiPF₆) is ubiquitous in commercial lithium-ion batteries, but it is hydrolytically unstable and corrosive on electrode surfaces. Using a more stable salt would confer multiple benefits for high-voltage operation, but many such electrolyte systems facilitate anodic dissolution and pitting corrosion of aluminum current collectors that negate their advantages. Lithium 2-trifluoromethyl-4,5-dicyanoimidazolide (LiTDI) is a new salt that was designed specifically for high-voltage cells. In this study we demonstrate that in carbonate electrolytes, LiTDI prevents anodic dissolution of Al current collectors, which places it into a select group of corrosion inhibitors. However, we also demonstrate that LiTDI becomes reduced on lithiated graphite, undergoing sequential defluorination and yielding a thick and resistive solid-electrolyte interphase (SEI), which increases impedance and lowers electrode capacity. The mechanistic causes for this behavior are examined using computational chemistry methods in the light of recent spectroscopic studies. Here, we demonstrate that LiTDI reduction can be prevented by certain electrolyte additives, which include fluoroethylene carbonate, vinylene carbonate and lithium bis(oxalato)borate. This beneficial action is due to preferential reduction of these additives over LiTDI at a higher potential vs. Li/Li⁺, so the resulting SEI can prevent the direct reduction of LiTDI at lower potentials on the graphite electrode.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1337946

Journal Information:: Journal of Physical Chemistry. C, Vol. 120, Issue 50; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 12 works

Citation information provided by
Web of Science

References (53)

Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries Xu, Kang Chemical Reviews, Vol. 104, Issue 10, p. 4303-4418 https://doi.org/10.1021/cr030203g	journal	October 2004
Electrolytes and Interphases in Li-Ion Batteries and Beyond Xu, Kang Chemical Reviews, Vol. 114, Issue 23 https://doi.org/10.1021/cr500003w	journal	October 2014
Allotropic Control: How Certain Fluorinated Carbonate Electrolytes Protect Aluminum Current Collectors by Promoting the Formation of Insoluble Coordination Polymers Shkrob, Ilya A.; Pupek, Krzysztof Z.; Abraham, Daniel P. The Journal of Physical Chemistry C, Vol. 120, Issue 33 https://doi.org/10.1021/acs.jpcc.6b05241	journal	August 2016
Surface reconstruction and chemical evolution of stoichiometric layered cathode materials for lithium-ion batteries Lin, Feng; Markus, Isaac M.; Nordlund, Dennis Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms4529	journal	March 2014
On the Electrochemical Behavior of Aluminum Electrodes in Nonaqueous Electrolyte Solutions of Lithium Salts Markovsky, Boris; Amalraj, Francis; Gottlieb, Hugo E. Journal of The Electrochemical Society, Vol. 157, Issue 4 https://doi.org/10.1149/1.3294774	journal	January 2010
Role of the LiPF ₆ Salt for the Long-Term Stability of Silicon Electrodes in Li-Ion Batteries – A Photoelectron Spectroscopy Study Philippe, Bertrand; Dedryvère, Rémi; Gorgoi, Mihaela Chemistry of Materials, Vol. 25, Issue 3 https://doi.org/10.1021/cm303399v	journal	January 2013
Influence of inactive electrode components on degradation phenomena in nano-Si electrodes for Li-ion batteries Jeschull, Fabian; Lindgren, Fredrik; Lacey, Matthew J. Journal of Power Sources, Vol. 325 https://doi.org/10.1016/j.jpowsour.2016.06.059	journal	September 2016
SEI Formation and Interfacial Stability of a Si Electrode in a LiTDI-Salt Based Electrolyte with FEC and VC Additives for Li-Ion Batteries Lindgren, Fredrik; Xu, Chao; Niedzicki, Leszek ACS Applied Materials & Interfaces, Vol. 8, Issue 24 https://doi.org/10.1021/acsami.6b02650	journal	June 2016
A hard X-ray photoelectron spectroscopy study on the solid electrolyte interphase of a lithium 4,5-dicyano-2-(trifluoromethyl)imidazolide based electrolyte for Si-electrodes Lindgren, Fredrik; Xu, Chao; Maibach, Julia Journal of Power Sources, Vol. 301 https://doi.org/10.1016/j.jpowsour.2015.09.112	journal	January 2016
Issues and challenges facing rechargeable lithium batteries Tarascon, J.-M.; Armand, M. Nature, Vol. 414, Issue 6861, p. 359-367 https://doi.org/10.1038/35104644	journal	November 2001
Building better batteries Armand, M.; Tarascon, J.-M. Nature, Vol. 451, Issue 7179, p. 652-657 https://doi.org/10.1038/451652a	journal	February 2008
Recent progress in high-voltage lithium ion batteries Hu, Meng; Pang, Xiaoli; Zhou, Zhen Journal of Power Sources, Vol. 237 https://doi.org/10.1016/j.jpowsour.2013.03.024	journal	September 2013
Lithium bis(fluorosulfonyl)imide (LiFSI) as conducting salt for nonaqueous liquid electrolytes for lithium-ion batteries: Physicochemical and electrochemical properties Han, Hong-Bo; Zhou, Si-Si; Zhang, Dai-Jun Journal of Power Sources, Vol. 196, Issue 7 https://doi.org/10.1016/j.jpowsour.2010.12.040	journal	April 2011
Transport and Electrochemical Properties and Spectral Features of Non-Aqueous Electrolytes Containing LiFSI in Linear Carbonate Solvents Li, Lifei; Zhou, Sisi; Han, Hongbo Journal of The Electrochemical Society, Vol. 158, Issue 2 https://doi.org/10.1149/1.3514705	journal	January 2011
Corrosion/passivation of aluminum current collector in bis(fluorosulfonyl)imide-based ionic liquid for lithium-ion batteries Cho, Erang; Mun, Junyoung; Chae, Oh B. Electrochemistry Communications, Vol. 22 https://doi.org/10.1016/j.elecom.2012.05.018	journal	August 2012
Corrosion of Aluminum Current Collectors in High-Power Lithium-Ion Batteries for Use in Hybrid Electric Vehicles Hyams, Tzipi Cohen; Go, John; Devine, Thomas M. Journal of The Electrochemical Society, Vol. 154, Issue 8 https://doi.org/10.1149/1.2742321	journal	January 2007
Electrochemical behavior and passivation of current collectors in lithium-ion batteries Myung, Seung-Taek; Hitoshi, Yashiro; Sun, Yang-Kook Journal of Materials Chemistry, Vol. 21, Issue 27 https://doi.org/10.1039/c0jm04353b	journal	January 2011
Aluminum Corrosion in Lithium Batteries An Investigation Using the Electrochemical Quartz Crystal Microbalance Yang, Haesik; Kwon, Kyungjung; Devine, Thomas M. Journal of The Electrochemical Society, Vol. 147, Issue 12 https://doi.org/10.1149/1.1394077	journal	January 2000
Suppression of aluminum current collector corrosion in ionic liquid containing electrolytes Kühnel, Ruben-Simon; Lübke, Mechthild; Winter, Martin Journal of Power Sources, Vol. 214 https://doi.org/10.1016/j.jpowsour.2012.04.054	journal	September 2012
Mechanism of Anodic Dissolution of the Aluminum Current Collector in 1 M LiTFSI EC:DEC 3:7 in Rechargeable Lithium Batteries Krämer, Elisabeth; Schedlbauer, Tanja; Hoffmann, Björn Journal of The Electrochemical Society, Vol. 160, Issue 2 https://doi.org/10.1149/2.081302jes	journal	December 2012
Current Collectors for Positive Electrodes of Lithium-Based Batteries Whitehead, Adam H.; Schreiber, Martha Journal of The Electrochemical Society, Vol. 152, Issue 11 https://doi.org/10.1149/1.2039587	journal	January 2005
New type of imidazole based salts designed specifically for lithium ion batteries Niedzicki, L.; Żukowska, G. Z.; Bukowska, M. Electrochimica Acta, Vol. 55, Issue 4, p. 1450-1454 https://doi.org/10.1016/j.electacta.2009.05.008	journal	January 2010
Lithium cation conducting TDI anion-based ionic liquids Niedzicki, Leszek; Karpierz, Ewelina; Zawadzki, Maciej Phys. Chem. Chem. Phys., Vol. 16, Issue 23 https://doi.org/10.1039/c3cp55354j	journal	January 2014
New covalent salts of the 4+V class for Li batteries Niedzicki, Leszek; Grugeon, Sylvie; Laruelle, Stéphane Journal of Power Sources, Vol. 196, Issue 20 https://doi.org/10.1016/j.jpowsour.2011.06.030	journal	October 2011
Optimization of the lithium-ion cell electrolyte composition through the use of the LiTDI salt Niedzicki, L.; Karpierz, E.; Bitner, A. Electrochimica Acta, Vol. 117 https://doi.org/10.1016/j.electacta.2013.11.134	journal	January 2014
LiTDI and solvent mixture based electrolytes for lithium-ion cells Niedzicki, L.; Brzozowski, B.; Wieczorek, P. Electrochimica Acta, Vol. 174 https://doi.org/10.1016/j.electacta.2015.06.038	journal	August 2015
The AHA Moment: Assessment of the Redox Stability of Ionic Liquids Based on Aromatic Heterocyclic Anions (AHAs) for Nuclear Separations and Electric Energy Storage Shkrob, Ilya A.; Marin, Timothy W. The Journal of Physical Chemistry B, Vol. 119, Issue 46 https://doi.org/10.1021/acs.jpcb.5b09057	journal	November 2015
Anion Coordination Interactions in Solvates with the Lithium Salts LiDCTA and LiTDI McOwen, Dennis W.; Delp, Samuel A.; Paillard, Elie The Journal of Physical Chemistry C, Vol. 118, Issue 15 https://doi.org/10.1021/jp412601x	journal	April 2014
In-Depth Interfacial Chemistry and Reactivity Focused Investigation of Lithium–Imide- and Lithium–Imidazole-Based Electrolytes Eshetu, Gebrekidan Gebresilassie; Diemant, Thomas; Grugeon, Sylvie ACS Applied Materials & Interfaces, Vol. 8, Issue 25 https://doi.org/10.1021/acsami.6b04406	journal	June 2016
A review of the features and analyses of the solid electrolyte interphase in Li-ion batteries Verma, Pallavi; Maire, Pascal; Novák, Petr Electrochimica Acta, Vol. 55, Issue 22, p. 6332-6341 https://doi.org/10.1016/j.electacta.2010.05.072	journal	September 2010
Reduction of Carbonate Electrolytes and the Formation of Solid-Electrolyte Interface (SEI) in Lithium-Ion Batteries. 2. Radiolytically Induced Polymerization of Ethylene Carbonate Shkrob, Ilya A.; Zhu, Ye; Marin, Timothy W. The Journal of Physical Chemistry C, Vol. 117, Issue 38, p. 19270-19279 https://doi.org/10.1021/jp406273p	journal	September 2013
Reduction of Carbonate Electrolytes and the Formation of Solid-Electrolyte Interface (SEI) in Lithium-Ion Batteries. 1. Spectroscopic Observations of Radical Intermediates Generated in One-Electron Reduction of Carbonates Shkrob, Ilya A.; Zhu, Ye; Marin, Timothy W. The Journal of Physical Chemistry C, Vol. 117, Issue 38, p. 19255-19269 https://doi.org/10.1021/jp406274e	journal	September 2013
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density Lee, Chengteh; Yang, Weitao; Parr, Robert G. Physical Review B, Vol. 37, Issue 2 https://doi.org/10.1103/PhysRevB.37.785	journal	January 1988
Density-functional exchange-energy approximation with correct asymptotic behavior Becke, A. D. Physical Review A, Vol. 38, Issue 6 https://doi.org/10.1103/PhysRevA.38.3098	journal	September 1988
On the performance of the semiempirical quantum mechanical PM6 and PM7 methods for noncovalent interactions Hostaš, Jiří; Řezáč, Jan; Hobza, Pavel Chemical Physics Letters, Vol. 568-569 https://doi.org/10.1016/j.cplett.2013.02.069	journal	May 2013
Optimization of parameters for semiempirical methods VI: more modifications to the NDDO approximations and re-optimization of parameters Stewart, James J. P. Journal of Molecular Modeling, Vol. 19, Issue 1 https://doi.org/10.1007/s00894-012-1667-x	journal	November 2012
GPU Linear Algebra Libraries and GPGPU Programming for Accelerating MOPAC Semiempirical Quantum Chemistry Calculations Maia, Julio Daniel Carvalho; Urquiza Carvalho, Gabriel Aires; Mangueira, Carlos Peixoto Journal of Chemical Theory and Computation, Vol. 8, Issue 9 https://doi.org/10.1021/ct3004645	journal	August 2012
Exceptional chemical and thermal stability of zeolitic imidazolate frameworks Park, K. S.; Ni, Z.; Cote, A. P. Proceedings of the National Academy of Sciences, Vol. 103, Issue 27, p. 10186-10191 https://doi.org/10.1073/pnas.0602439103	journal	June 2006
Synthesis, Structure, and Carbon Dioxide Capture Properties of Zeolitic Imidazolate Frameworks Phan, Anh; Doonan, Christian J.; Uribe-Romo, Fernando J. Accounts of Chemical Research, Vol. 43, Issue 1, p. 58-67 https://doi.org/10.1021/ar900116g	journal	January 2010
Indium Imidazolate Frameworks with Differently Distorted ReO ₃ -Type Structures: Syntheses, Structures, Phase Transitions, and Crystallization Studies Schweinefuß, Maria E.; Baburin, Igor A.; Schröder, Christian A. Crystal Growth & Design, Vol. 14, Issue 9 https://doi.org/10.1021/cg5007499	journal	August 2014
Ln-Imidazolate Frameworks: The Coordinative Demand of Ln ³⁺ Ions and its Consequences for the Compound Constitution of Different Lanthanides Zurawski, Alexander; Rybak, Jens-Christoph; Meyer, Larissa V. Zeitschrift für anorganische und allgemeine Chemie, Vol. 639, Issue 2 https://doi.org/10.1002/zaac.201200428	journal	November 2012
Thiourea Derivatives as Potent Inhibitors of Aluminum Corrosion: Atomic-Level Insight into Adsorption and Inhibition Mechanisms Weder, Nicola; Alberto, Roger; Koitz, Ralph The Journal of Physical Chemistry C, Vol. 120, Issue 3 https://doi.org/10.1021/acs.jpcc.5b11750	journal	January 2016
Electrochemical and molecular dynamics simulation studies on the corrosion inhibition of aluminum in molar hydrochloric acid using some imidazole derivatives Khaled, K. F.; Amin, Mohammed A. Journal of Applied Electrochemistry, Vol. 39, Issue 12 https://doi.org/10.1007/s10800-009-9951-x	journal	June 2009
Effect of electrolyte composition on initial cycling and impedance characteristics of lithium-ion cells Abraham, D. P.; Furczon, M. M.; Kang, S. -H. Journal of Power Sources, Vol. 180, Issue 1 https://doi.org/10.1016/j.jpowsour.2008.02.047	journal	May 2008
Mechanistic Insight into the Protective Action of Bis(oxalato)borate and Difluoro(oxalate)borate Anions in Li-Ion Batteries. Shkrob, Ilya A.; Zhu, Ye; Marin, Timothy W. The Journal of Physical Chemistry C, Vol. 117, Issue 45 https://doi.org/10.1021/jp407714p	journal	October 2013
Why Bis(fluorosulfonyl)imide Is a “Magic Anion” for Electrochemistry Shkrob, Ilya A.; Marin, Timothy W.; Zhu, Ye The Journal of Physical Chemistry C, Vol. 118, Issue 34 https://doi.org/10.1021/jp506567p	journal	August 2014
What Makes Fluoroethylene Carbonate Different? Shkrob, Ilya A.; Wishart, James F.; Abraham, Daniel P. The Journal of Physical Chemistry C, Vol. 119, Issue 27 https://doi.org/10.1021/acs.jpcc.5b03591	journal	June 2015
The state of understanding of the lithium-ion-battery graphite solid electrolyte interphase (SEI) and its relationship to formation cycling An, Seong Jin; Li, Jianlin; Daniel, Claus Carbon, Vol. 105 https://doi.org/10.1016/j.carbon.2016.04.008	journal	August 2016
In Situ and Quantitative Characterization of Solid Electrolyte Interphases Cresce, Arthur v.; Russell, Selena M.; Baker, David R. Nano Letters, Vol. 14, Issue 3 https://doi.org/10.1021/nl404471v	journal	February 2014
Modeling Electrochemical Decomposition of Fluoroethylene Carbonate on Silicon Anode Surfaces in Lithium Ion Batteries Leung, Kevin; Rempe, Susan B.; Foster, Michael E. Journal of The Electrochemical Society, Vol. 161, Issue 3 https://doi.org/10.1149/2.092401jes	journal	December 2013
Reduction Mechanisms of Ethylene Carbonate on Si Anodes of Lithium-Ion Batteries: Effects of Degree of Lithiation and Nature of Exposed Surface Martinez de la Hoz, Julibeth M.; Leung, Kevin; Balbuena, Perla B. ACS Applied Materials & Interfaces, Vol. 5, Issue 24 https://doi.org/10.1021/am404365r	journal	November 2013
Effect of the Electrolyte Composition on SEI Reactions at Si Anodes of Li-Ion Batteries Martinez de la Hoz, Julibeth M.; Soto, Fernando A.; Balbuena, Perla B. The Journal of Physical Chemistry C, Vol. 119, Issue 13 https://doi.org/10.1021/acs.jpcc.5b01228	journal	March 2015
Reduction mechanisms of additives on Si anodes of Li-ion batteries Martínez de la Hoz, Julibeth M.; Balbuena, Perla B. Phys. Chem. Chem. Phys., Vol. 16, Issue 32 https://doi.org/10.1039/C4CP01948B	journal	January 2014

Cited By (2)

The Role of LiTDI Additive in LiNi _1/3 Mn _1/3 Co _1/3 O ₂ /Graphite Lithium-Ion Batteries at Elevated Temperatures Xu, Chao; Jeschull, Fabian; Brant, William R. Journal of The Electrochemical Society, Vol. 165, Issue 2 https://doi.org/10.1149/2.0231802jes	journal	January 2018
Chemically soft solid electrolyte interphase forming additives for lithium-ion batteries Jankowski, Piotr; Poterała, Marcin; Lindahl, Niklas Journal of Materials Chemistry A, Vol. 6, Issue 45 https://doi.org/10.1039/c8ta07936f	journal	January 2018

Similar Records

Eeffect of electrolyte composition on initial cycling and impedance characteristics of lithium-ion-cells.

Journal Article · Tue Jan 01 00:00:00 EST 2008 · J. Power Sources · OSTI ID:1337946

Abraham, D P; Furczon, M M; Kang, S -H; +2 more

Improved Low Temperature Performance of Graphite/Li Cells Using Isoxazole as a Novel Cosolvent in Electrolytes

Journal Article · Wed Jul 14 00:00:00 EDT 2021 · Journal of the Electrochemical Society · OSTI ID:1337946

Rodrigo, Nuwanthi D.; Tan, Sha; Shadike, Zulipiya; +3 more

Use of Ethylene Carbonate Free Ester Solvent Systems with Alternative Lithium Salts for Improved Low-Temperature Performance in NCM622∣∣ Graphite Li-ion Batteries

Journal Article · Thu Nov 03 00:00:00 EDT 2022 · Journal of the Electrochemical Society · OSTI ID:1337946

Rodrigo, Nuwanthi D.; Jayawardana, Chamithri; Rynearson, Leah; +3 more

Related Subjects

25 ENERGY STORAGE
lithium battery
solid electrolyte interphase

Title: Chemical stability of Lithium 2-trifluoromethyl-4,5-dicyanoimidazolide, an electrolyte salt for Li-ion cells

Citation Formats

References (53)

Cited By (2)

Similar Records

Related Subjects