Li<sup>+</sup> Transport in Lithium Sulfonylimide−Oligo(ethylene oxide) Ionic Liquids and Oligo(ethylene oxide) Doped with LiTFSI

Borodin, Oleg; Smith, Grant D.; Geiculescu, Olt E.; Creager, Stephen E.; Hallac, Boutros B.; DesMarteau, Darryl D.

doi:10.1021/jp0653104

Cited by 56 publications

(71 citation statements)

References 42 publications

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“…MD simulations were used to study a number of electrolytes of potential interest to lithium battery applications: EC:DMC/LiPF 6 [52], EC/LiTFSI [53,54], DMC/ LiTFSI [55], GBL/LiTFSI [55], and acetonitrile doped with LiPF 6 , LiClO 4 , LiBF 4 , LiDFOB, LiTFSI [56][57][58], oligoethers/Li salts [59][60][61], acetamide/LiTFSI [62], EC/LiBF 4 [63], PC/LiBF 4 [63,64], PC/LiPF 6 [64], DMC/LiBF 4 [63], oligoethers/ LiPF 6 [65][66][67], and PC/LiTFSI [54]. Most simulations focused on understanding the lithium cation coordination by solvent molecules and cation-anion aggregation.…”

Section: Organic Liquid Electrolytesmentioning

confidence: 99%

“…MD simulations [59,98] employing classical polarizable force fields have been used to investigate the structure and transport of two SEI components: dilithium ethylene dicarbonate (LiCO 3 CH 2 ) 2 , or Li 2 EDC, and LiMC, which are often found in outer part of the SEI [99,100]. While crystals are of room temperature, these compounds might exist in a disordered state in the outer part of the SEI because the high fraction of other components and impurities that might present in the SEI would inhibit the formation of the crystalline ordered phase.…”

Section: Modeling Of Sei Componentsmentioning

confidence: 99%

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Molecular Modeling of Electrolytes

Borodin

2014

Modern Aspects of Electrochemistry

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Recent advances in molecular modeling provide significant insight into electrolyte electrochemical and transport properties. The first part of the chapter discusses applications of quantum chemistry methods to determine electrolyte oxidative stability and oxidation-induced decomposition reactions. A link between the oxidation stability of model electrolyte clusters and the kinetics of oxidation reactions is established and compared with the results of linear sweep voltammetry measurements. The second part of the chapter focuses on applying molecular dynamics (MD) simulations and density functional theory to predict the structural and transport properties of liquid electrolytes and solid electrolyte interphase (SEI) model compounds; the free energy profiles for lithium desolvation from electrolytes; and the behavior of electrolytes at charged electrodes and the electrolyte-SEI interface.

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Section: Organic Liquid Electrolytesmentioning

confidence: 99%

Section: Modeling Of Sei Componentsmentioning

confidence: 99%

Molecular Modeling of Electrolytes

Borodin

2014

Modern Aspects of Electrochemistry

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“…33,34 This idea of charge delocalization on perfluorinated sulfonimide group was initially addressed by the Watanabe and DesMarteau groups. 35,36 Armand et al have demonstrated the synthesis of poly(Sty-Tf 2 N) neutralized with lithium ions and blended with PEO to form single-ion polymer electrolytes for lithium batteries. Ion conductivities were approximately 10 times higher for a membrane with poly(Sty-Tf 2 N) (∼10 −6 S/cm at 70°C) compared to a membrane with lithium poly-(styrenesulfonate).…”

Section: ■ Introductionmentioning

confidence: 99%

Sulfonimide-Containing Triblock Copolymers for Improved Conductivity and Mechanical Performance

et al. 2015

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Ion-containing block copolymers continue to attract significant interest as conducting membranes in energy storage devices. Reversible addition−fragmentation chain transfer (RAFT) polymerization enables the synthesis of well-defined ionomeric A−BC−A triblock copolymers, featuring a microphase-separated morphology and a combination of excellent mechanical properties and high ion transport. The soft central "BC" block is composed of poly(4-styrenesulfonyl-(trifluoromethylsulfonyl)imide) (poly(Sty-Tf 2 N)) with −SO 2 −N − −SO 2 −CF 3 anionic groups associated with a mobile lithium cation and low-T g di(ethylene glycol)methyl ether methacrylate (DEGMEMA) units. External polystyrene A blocks provide mechanical strength with nanoscale morphology even at high ion content. Electrochemical impedance spectroscopy (EIS) and pulse-field-gradient (PFG) NMR spectroscopy have clarified the ion transport properties of these ionomeric A−BC−A triblock copolymers. Results confirmed that well-defined ionomeric A−BC−A triblock copolymers combine improved ion-transport properties with mechanical stability with significant potential for application in energy storage devices.

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“…The anion predominately favored for this work is the bis͑trifluoromethanesulfonyl͒imide ͑TFSI͒ anion, which generally forms hydrophobic ionic liquids. 24,25 Presented here is a comparative study of polymer gel electrolytes using a hydrophobic and hydrophilic polymer, PEO and PVdF-FHP, respectively; and a hydrophobic and hydrophilic type of ionic liquid, 1-n-propyl-2,3-dimethylimidazolium tetrafluoroborate ͑MMPIBF 4 ͒ and 1-npropyl-2,3-dimethylimidazolium hexafluorophosphate ͑MMPIPF 6 ͒, respectively. These two specific ionic liquids where chosen as representatives of many types of paired hydrophobic-hydrophilic ionic liquids.…”

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confidence: 99%

Hydrophobic and Hydrophilic Interactions of Ionic Liquids and Polymers in Solid Polymer Gel Electrolytes

Sutto

2007

J. Electrochem. Soc.

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Poly͑ethylene oxide͒, PEO, or poly͑vinylidenefluoride-co-hexafluoropropene͒, PVdF-HFP, and the ionic liquids 1-n-propyl-2,3-dimethylimidazolium tetrafluoroborate ͑MMPIBF 4 ͒ and 1-n-propyl-2,3-dimethylimidazolium hexafluorophosphate ͑MMPIPF 6 ͒ with and without 0.5 M Li salt were used to prepare solid polymer gel electrolytes. Experimentation indicates that for the PEO films, the 20 and 30 wt % polymer gels exhibited the highest ionic conductivity, although the 20 wt % film is fragile and exhibits poor mechanical properties. Therefore, the composition of all gels studied is 30 wt % polymer and 70 wt % ionic liquid. For all systems, addition of the lithium salts results in approximately a 33% drop in ionic conductivity. Results indicate that for the formation of polymer gel electrolytes, selection of a nonpolar polymer paired with a hydrophobic electrolyte results in greater ionic conductivity and reversibility in the intercalation of Li ion into graphite. These results are interpreted in terms of the type of solid solution formed between the hydrophobic and hydrophilic polymers and the ionic liquids.In order to significantly improve the utility and resilience of the lithium or lithium-ion battery, solid polymer electrolytes have been extensively studied for use in safer, solid-state power sources. 1 Unfortunately, these solid polymers are typically very poor ion conductors at room temperature. 2,3 In order to overcome this deficit, polymer gel composite electrolytes, in which a liquid electrolyte or plasticizer is added to the polymer, have been extensively studied. These polymer composite gel electrolytes, prepared from a variety of polymers and electrolytes, such as the various organic carbonates, exhibit significantly enhanced ionic conductivity. 4-6 However, the use of these liquid components reintroduces the significant problems of flammability and volatility. 7,8 In order to overcome these problems, it is proposed that the use of nonflammable and nonvolatile ionic liquids in polymer composite gel electrolytes should allow for the formation of much safer polymer gel electrolytes for Li-ion solid-state batteries. [9][10][11][12][13][14][15] Ionic liquids, salts that are liquid at or below room temperature, have been extensively studied for their numerous unique physical and electrochemical properties. 16 However, unlike most common electrolytes, ionic liquids themselves are composed of a cationic and anionic species, and experimental evidence has shown that a simple battery can be formed from an ionic liquid and two graphitic electrodes, where the cation and anion of the ionic liquid are the currentcarrying, intercalative species. 17,18 These dual-intercalating molten electrolyte ͑DIME͒ batteries can also be prepared as solid-state batteries using a solid polymer-ionic liquid composite electrolyteseparator composed of an ionic liquid and poly͓vinylidene fluorideco-hexafluoropropene, PVdF-HFP ͑trade name Kynar 2801, average molar mass, M w of 380.000 g/mol and 11-12% of HFP comonomer, melting point 165°C͔͒. [1...

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Li⁺ Transport in Lithium Sulfonylimide−Oligo(ethylene oxide) Ionic Liquids and Oligo(ethylene oxide) Doped with LiTFSI

Cited by 56 publications

References 42 publications

Molecular Modeling of Electrolytes

Molecular Modeling of Electrolytes

Sulfonimide-Containing Triblock Copolymers for Improved Conductivity and Mechanical Performance

Hydrophobic and Hydrophilic Interactions of Ionic Liquids and Polymers in Solid Polymer Gel Electrolytes

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Li+ Transport in Lithium Sulfonylimide−Oligo(ethylene oxide) Ionic Liquids and Oligo(ethylene oxide) Doped with LiTFSI

Cited by 56 publications

References 42 publications

Molecular Modeling of Electrolytes

Molecular Modeling of Electrolytes

Sulfonimide-Containing Triblock Copolymers for Improved Conductivity and Mechanical Performance

Hydrophobic and Hydrophilic Interactions of Ionic Liquids and Polymers in Solid Polymer Gel Electrolytes

Contact Info

Product

Resources

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Li⁺ Transport in Lithium Sulfonylimide−Oligo(ethylene oxide) Ionic Liquids and Oligo(ethylene oxide) Doped with LiTFSI