Novel bis(fluorosulfonyl)imide-based and ether-functionalized ionic liquids for lithium batteries with improved cycling properties

Tsurumaki, Akiko; Ohno, Hiroyuki; Panero, S.; Navarra, Maria Assunta

doi:10.1016/j.electacta.2018.09.205

Cited by 30 publications

(32 citation statements)

References 35 publications

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“…The N -ethoxyethyl- N -methylpiperidinium FSI and N -ethoxyethyl- N -methylmorpholinium FSI ILs mixed with LiFSI in a 9:1 molar ratio electrolyte decomposed at 266 °C. These electrolytes presented acceptable ionic conductivity and a suitable electrochemical window with an ability to develop solid electrolyte interfaces on the electrode surfaces . The effect of the anion size on the ionic conductivity of the 1-butyl-3-methylimidazolium cation with six different anions including Cl – , Br – , I – , NCS – , NCN 2 – , and BF 4 – is also reported .…”

Section: Resultsmentioning

confidence: 97%

“…These electrolytes presented acceptable ionic conductivity and a suitable electrochemical window with an ability to develop solid electrolyte interfaces on the electrode surfaces. 85 The effect of the anion size on the ionic conductivity of the 1-butyl-3methylimidazolium cation with six different anions including Cl − , Br − , I − , NCS − , NCN 2 − , and BF 4 − is also reported. 86 The ionic conductivity increases with increasing anion size, which can be understood from the increase in the anion−cation interaction strength with the ion sizes.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Ion Transport and Electrochemical Properties of Fluorine-Free Lithium-Ion Battery Electrolytes Derived from Biomass

Khan

Гнездилов

Филиппов

et al. 2021

ACS Sustainable Chem. Eng.

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Unlike conventional electrolytes, ionic liquid (IL)-based electrolytes offer higher thermal stability, acceptable ionic conductivity, and a higher electrochemical stability window (ESW), which are indispensable for the proper functioning of Li-ion batteries. In this study, fluorine-free electrolytes are prepared by mixing the lithium furan-2-carboxylate [Li(FuA)] salt with the tetra(n-butyl)phosphonium furan-2-carboxylate [(P 4444 )(FuA)] IL in different molar ratios. The anion of these electrolytes is produced from biomass and agricultural waste on a large scale and, therefore, this study is a step ahead toward the development of renewable electrolytes for batteries. The electrolytes are found to have T onset higher than 568 K and acceptable ionic conductivities in a wide temperature range. The pulsed field gradient nuclear magnetic resonance (PFG-NMR) analysis has confirmed that the (FuA) − anion diffuses faster than the (P 4444 ) + cation in the neat (P 4444 )(FuA) IL; however, the anion diffusion becomes slower than cation diffusion by doping Li salt. The Li + ion interacts strongly with the carboxylate functionality in the (FuA) − anion and diffuses slower than other ions over the whole studied temperature range. The interaction of the Li + ion with the carboxylate group is also confirmed by 7 Li NMR and Fourier transform infrared (FTIR) spectroscopy. The transference number of the Li + ion is increased with increasing Li salt concentration. Linear sweep voltammetry (LSV) suggests lithium underpotential deposition and bulk reduction at temperatures above 313 K.

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Section: Resultsmentioning

confidence: 97%

Section: ■ Results and Discussionmentioning

confidence: 99%

Ion Transport and Electrochemical Properties of Fluorine-Free Lithium-Ion Battery Electrolytes Derived from Biomass

Khan

Гнездилов

Филиппов

et al. 2021

ACS Sustainable Chem. Eng.

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“…Cell batteries with these ILs were assembled and showed a nominal capacity of 150 mAh g −1 at C/10 (1 C was 1.08 mA cm −2 ) while retaining flat potential profiles throughout 50 cycles. [ 99 ]…”

Section: Ionic Liquid‐based Polymer Composites and Their Applicationsmentioning

confidence: 99%

Ionic Liquid–Polymer Composites: A New Platform for Multifunctional Applications

Correia

Fernandes

Martins

et al. 2020

Adv Funct Materials

238

201

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Ionic liquids (ILs) have emerged as a novel class of chemical compounds for the development of advanced (multi)functional materials with outstanding potential in applications of several areas due to their unique properties and functionalities. The combination of ILs with polymers, in a composite, allows for developing smart materials, which synergistically combine the features of specific polymers and ILs. Moreover, ILs can be extensively modified by the incorporation of functional groups with specific properties into the cation, anion, or both. Thus, it is possible to tune the IL, the polymer, or both to obtain a broad spectrum of multifunctional composites and address the specific requirements of many applications. This work focusses on advanced materials and strategies concerning ILs and polymers for the development of smart IL/polymer‐based materials for applications including responsive and sensitive sensors, actuators, environment, batteries, fuel cells, and biomedical applications.

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“…Room-temperature ionic liquids (RTILs) have been identified as potential candidates to replace traditional organic solvents due to their low flammability, relatively high ionic conductivity, and thermal and chemical stability at higher temperatures when compared to organic solvents. , Previous studies have used ILs based on the bis(trifluoromethanesulfonyl)imide ([TFSI] − ) or bis(fluorosulfonyl)imide ([FSI] − ) anion due to their high ionic conductivities and electrochemical stability during reversible Li + /Li 0 deposition (attributed to their wide electrochemical window). , It should be noted here that [TFSI] − , [NTf 2 ] − , and [Tf 2 N] − are all common abbreviations used for the bis(trifluoromethanesulfonyl)imide anion found in the literature. The cations most commonly used with these anions include pyrrolidinium ([Pyr nn ] + ) ILs, , piperidinium, ,− phosphonium, , and imidazolium (Im). − The utilization of imidazolium cation-based ionic liquids in LMB cells remains debatable, with previous studies ,, determining the neat 1-ethyl-1-methylimidazolium ([EMIm] + ) ILs to have an insufficient cathodic limiting potential of around +1.0 V versus Li/Li + . The acidic proton located on the C-2 carbon of the Im ring results in poor cathodic stability for these Im cations, compared to pyrrolidinium. , Schmitz et al previously demonstrated both [EMIm][TFSI] and 1-butyl-3-methylimidazolium [TFSI] − neat ILs to be chemically unstable against Li metal, in contrast to the [Pyr 14 ] + cation .…”

Section: Introductionmentioning

confidence: 99%

Stability of Boronium Cation-Based Ionic Liquid Electrolytes on the Li Metal Anode Surface

Clarke-Hannaford

Breedon

Rüther

et al. 2020

ACS Appl. Energy Mater.

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Augmented cycling performance in lithium metal batteries is often attributed to the formation of a stable solid electrolyte interphase (SEI) layer that forms on the Li surface. Boronium cation-based ionic liquid (trimethylamine)(dimethylethylamine)dihydroborate bis(trifluoromethanesulfonyl)imide, [NNBH2][TFSI], has shown stable cycling in a Li|LiFePO4 cell; however, it is not known why this ionic liquid performs well nor what species contribute to the SEI layer formation. To gain an understanding of the SEI layer that forms using boronium cation-based ILs, the chemical stability and reaction mechanisms occurring between [NNBH2][TFSI] and [NNBH2] bis(fluorosulfonyl)imide [FSI] with the Li(001) surface are investigated using a combination of density functional theory (DFT) calculations and ab initio molecular dynamics (AIMD) simulations at 298, 358, and 428 K. These simulations showed that the surface interaction with the cation is weak, while both the [FSI]− and [TFSI]− anions readily dissociate, forming several chemical species (including LiF, Li2O, and Li2S), with the dissociation of [FSI]− occurring at a lower temperature. The absence of cation dissociation at elevated temperatures implies that the initial stages of SEI formation are restricted to the reaction products from the anions studied. This work provides further evidence that the [NNBH2]+ cation is stable against a lithium metal surface, with the spontaneous decomposition of the cation unlikely to occur.

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Novel bis(fluorosulfonyl)imide-based and ether-functionalized ionic liquids for lithium batteries with improved cycling properties

Cited by 30 publications

References 35 publications

Ion Transport and Electrochemical Properties of Fluorine-Free Lithium-Ion Battery Electrolytes Derived from Biomass

Ion Transport and Electrochemical Properties of Fluorine-Free Lithium-Ion Battery Electrolytes Derived from Biomass

Ionic Liquid–Polymer Composites: A New Platform for Multifunctional Applications

Stability of Boronium Cation-Based Ionic Liquid Electrolytes on the Li Metal Anode Surface

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