On the Performances of Ionic Liquid-Based Electrolytes for Li-NMC Batteries

Chaudoy, Victor; Ghamouss, Fouad; Jacquemin, Johan; Houdbert, Jean-Christophe; Tran‐Van, François

doi:10.1007/s10953-015-0315-3

Cited by 14 publications

(9 citation statements)

References 46 publications

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“…To evaluate the ionicity of the reported electrolytes, that is, state of ionization of each IL, a classical Walden rule diagram was used. This approach allows evaluating the state of ionization of ILs and classifying them according to the position in the Walden plot. , The Walden rule correlates the logarithm of molar conductivity (Λ) and the logarithm of fluidity (1/η) through a temperature-dependent constant ( k ), as reported in Figure a and b.…”

Section: Resultsmentioning

confidence: 99%

“…The distance from the line and the position of the set of point on the graph suggests that both ILs, according to the Walden representation, are closer to the "good" IL zone. 29,30 Another way to present the Walden plot is shown in Figure 4b The conductivities reported for these ILs at 298 K are 6.9, 31 3.0, 19 3.0, 32 3.58, 17 1.73, 17 , respectively. Unlike the viscosity the comparison of the obtained conductivities with the literature seems to have higher differences which are assigned to the more sensitivity of EIS to systematic error.…”

Section: Mpa•s For [Bmpyr][fsi] [P 2225 ][ Fsi] [Bmpyr] [Tfsi] [P 222...mentioning

confidence: 99%

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A Comparison among Viscosity, Density, Conductivity, and Electrochemical Windows of N-n-Butyl-N-methylpyrrolidinium and Triethyl-n-pentylphosphonium Bis(fluorosulfonyl imide) Ionic Liquids and Their Analogues Containing Bis(trifluoromethylsulfonyl) Imide Anion

et al. 2017

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Ionic liquid consists of an organic cation and generally an inorganic anion. The properties of liquids can be modulated by changing the anion or the cation or both. Two ionic liquids derived from the anion [FSI] were synthesized and characterized: (N-n-butyl-N-methylpyrrolidinium bis-(fluorosulfonyl imide), [BMPYR][FSI]) and triethyl-n-pentylphosphonium bis(fluorosulfonyl)imide), [P 2225 ][FSI]). We also report the comparison with [TFSI] based ionic liquids, namely: (N-n-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide), [BMPYR][TFSI]), (N-n-butyl-N-methylpiperidinium bis(trifluoromethylsulfonyl)imide), [BMP][TFSI]), triethyl-npentylphosphonium bis(trifluoromethylsulfonyl)imide), [P 2225 ][TFSI]) and (triethyl(2-methoxyethyl) phosphonium bis(trifluoromethylsulfonyl imide), [P 222201 ][TFSI]. Thermophysical properties, such as viscosity (298.15−373.15 K), density (298.15−373.15 K), conductivity (298.15−361.15 K), electrochemical (cutoff density current within 150 μA•cm −2 ), and thermal stability (303.15−973.15 K) were experimentally determined. The results showed that [FSI] derivatives exhibit better transport properties and lower thermal and electrochemical stability when compared with their [TFSI] counterparts.

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Section: Resultsmentioning

confidence: 99%

Section: Mpa•s For [Bmpyr][fsi] [P 2225 ][ Fsi] [Bmpyr] [Tfsi] [P 222...mentioning

confidence: 99%

A Comparison among Viscosity, Density, Conductivity, and Electrochemical Windows of N-n-Butyl-N-methylpyrrolidinium and Triethyl-n-pentylphosphonium Bis(fluorosulfonyl imide) Ionic Liquids and Their Analogues Containing Bis(trifluoromethylsulfonyl) Imide Anion

et al. 2017

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“…[16,17] Room-temperature ionic liquids (ILs) are molten salts that can be used as an alternative solvent for organic solvents for various types of batteries. [7,13,[18][19][20] Consisting of anions and cations with delocalized charges and sterically demanding side groups and thus weak intermolecular interactions, ILs have an almost negligible vapor pressure. [21] Therefore, issues related to the flammability or volatility of electrolytes are considered insignificant for such cell chemistries.…”

Section: Introductionmentioning

confidence: 99%

Galvanic Couples in Ionic Liquid‐Based Electrolyte Systems for Lithium Metal Batteries—An Overlooked Cause of Galvanic Corrosion?

Dohmann

Horsthemke

Küpers

et al. 2021

Advanced Energy Materials

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changes of our transportation and energy storage systems. [1] During recent decades, tremendous efforts were devoted toward the development, establishment, and improvement of electromobility. [2,3] Key requirements to render electromobility more competitive with conventional internal combustion technologies are commonly seen as improvements toward the battery. [4] Whereas the development of conventional lithium ion battery (LIB) technology is already well advanced, improvements toward properties such as energy density, sustainability, and safety remain highly desirable to encourage mass adoption of electromobility. [5] Stateof-the-art LIBs typically contain different types of carbon (e.g., graphitic, hard, soft, or amorphous carbons) and/or silicon as negative electrode materials. [6][7][8] A shift toward lithium metal-based batteries (LMBs) is often considered a desirable option for improvements of overall cell capacities and energy densities due to its high specific capacity (3860 mAh g −1 ) and low standard reduction potential (−3.04 V vs standard hydrogen electrode). [2,9] Nevertheless, the strong benefit of the electrochemical characteristics renders Li metal a key technology for the next evolutional step of batteries which includes the combination of Li with other high capacity materials at the positive electrode side. Novel key technologies like the utilization The breakthroughs in rechargeable lithium metal-anode-based batteries is still challenged by safety and performance limitations. Ionic liquid (IL)-based electrolytes are in consideration for increased safety but their moderate electrolyte performance and high costs still suppress their usefulness in Li metal-batteries. In an effort to deepen the understanding of the limited performance, galvanic corrosion as an electrochemical degradation process is herein identified as a contributing factor toward battery cell deterioration. Four different ILs, based on bis(trifluoromethylsulfonyl)imide in combination with the quaternary ammonium cations N-butyl-N-methylpyrrolidinium, N-methyl-N-propyl-pyrrolidinium, N-butyl-N-methylpiperidinium, and N-butyltrimethylammonium, respectively, are systematically investigated for such corrosive side reactions. The reaction pathways of this commonly neglected phenomenon are found to be both Hofmann-type and reductive eliminations. Supported by headspace-gas chromatography-mass spectrometry, the evolving gaseous reaction products are characterized. With zero resistance ammetry and Li electrochemical dissolution and deposition experiments, the dependency of galvanic corrosion on the presence of the galvanically coupled materials is elucidated. Variation of the lithium bis(trifluoromethylsulfonyl)imide concentration in the electrolytes is shown to influence the extent of detectable degradation products. Based on these findings, the necessity for more sophisticated electrode designs and electrolyte formulations is emphasized.

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“…Furthermore, Li[TFSI] offers many advantages, such as a higher solubility in many solvents (including ILs), driven by a lower lattice energy than the benchmarks Li[PF 6 ] or Li [BF 4 ] [18]. Therefore, many studies investigating the use of IL-Li[TFSI] mixtures as electrolytes for Li-batteries have been reported [19][20][21][22][23][24]. However, only a few studies have been conducted by mixing salts to yield both [FSI] − and [TFSI] − anions in solution.…”

Section: Introductionmentioning

confidence: 99%

Effect of mixed anions on the transport properties and performance of an ionic liquid-based electrolyte for lithium-ion batteries

Chaudoy

Jacquemin

Tran‐Van

et al. 2019

Pure and Applied Chemistry

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In this work, the physical, transport and electrochemical properties of various electrolytic solutions containing the 1-propyl-1-methylpyrrolidinium bis[fluorosulfonyl]imide ([C3C1pyr][FSI]) mixed with the lithium bis[(trifluoromethyl)sulfonyl]imide (Li[TFSI]) over a wide range of compositions are reported as a function of temperature at atmospheric pressure. First, the ionicity, lithium transference number, and transport properties (viscosity and conductivity) as well as the volumetric properties (density and molar volume) were determined as a function of lithium salt concentration from 293 to 343 K. Second, the self-diffusion coefficient of each ion in solution was measured by nuclear magnetic resonance (NMR) spectroscopy with pulsed field gradients (PFG). Moreover, an analysis of the collected nuclear Overhauser effect (NOE) data along with ab initio and COSMO-RS calculations was conducted to depict intra and intermolecular neighbouring within the electrolytic mixtures. Based on this analysis, and as expected, all activation energies increase with the Li[TFSI] concentration in solution, and all activation energies were determined from the self-diffusion data for all ions. Interestingly, regardless of the composition in solution, these activation energies were similar, except for those determined for the [FSI]− anion. The activation energy of [FSI]− self-diffusion relatively decreases compared to the other ions as the lithium salt concentration increases. Furthermore, the lithium transference was strongly affected by the lithium salt concentration, reaching an optimal value and an ionicity of approximately 50 % at a molality close to 0.75 mol · kg−1. Finally, these electrolytes were used in lithium-ion batteries (i.e. Li/NMC and LTO/NMC), demonstrating a clear relationship between the electrolyte formulation, its transport parameters and battery performance.

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On the Performances of Ionic Liquid-Based Electrolytes for Li-NMC Batteries

Cited by 14 publications

References 46 publications

A Comparison among Viscosity, Density, Conductivity, and Electrochemical Windows of N-n-Butyl-N-methylpyrrolidinium and Triethyl-n-pentylphosphonium Bis(fluorosulfonyl imide) Ionic Liquids and Their Analogues Containing Bis(trifluoromethylsulfonyl) Imide Anion

A Comparison among Viscosity, Density, Conductivity, and Electrochemical Windows of N-n-Butyl-N-methylpyrrolidinium and Triethyl-n-pentylphosphonium Bis(fluorosulfonyl imide) Ionic Liquids and Their Analogues Containing Bis(trifluoromethylsulfonyl) Imide Anion

Galvanic Couples in Ionic Liquid‐Based Electrolyte Systems for Lithium Metal Batteries—An Overlooked Cause of Galvanic Corrosion?

Effect of mixed anions on the transport properties and performance of an ionic liquid-based electrolyte for lithium-ion batteries

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