LiTDI as electrolyte salt for Li-ion batteries: transport properties in EC/DMC

Berhaut, Christopher L.; Porion, Patrice; Timperman, Laure; Schmidt, Gudrun; Lemordant, Daniel; Anouti, Mérièm

doi:10.1016/j.electacta.2015.08.165

Cited by 57 publications

(41 citation statements)

References 27 publications

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“…This Hückel anion is indeed less prone to hydrolysis and more thermally stable than PF 6 − . It also offers better protection than TFSI − to corrosion of the aluminum current collector ,. Given its melting point at ca.…”

Section: Introductionsupporting

confidence: 86%

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Electrolytes based on N‐Butyl‐N‐Methyl‐Pyrrolidinium 4,5‐Dicyano‐2‐(Trifluoromethyl) Imidazole for High Voltage Electrochemical Double Layer Capacitors

et al. 2018

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Owing to their exceptional electrochemical stability, ionic liquids (ILs) are highly promising electrolytes for high voltage electrochemical double layer capacitors (EDLCs). However, these molten salts often suffer from high viscosity and low conductivity, strongly affecting their application at room temperature. In this work the potential role of N‐butyl‐N‐methyl‐pyrrolidinium 4,5‐dicyano‐2‐(trifluoromethyl) imidazole (Pyr14TDI) as electrolyte component is evaluated for the first time. Although it is classified as an IL, its melting point at 48 °C hinders the use of the pure IL as solvent‐free electrolyte at medium‐to‐low temperatures. For this reason, mixtures with propylene carbonate (PC) are investigated to widen its temperature operation range (−30 to 60 °C). Different Pyr14TDI:PC ratios are investigated, from diluted solution (1 : 3 w/w) to solvent‐in‐salt (3 : 1 w/w). The properties of such electrolytes are determined in terms of viscosity, density, flash point, ionic conductivity, and electrochemical performance in EDLC. By proper electrode balancing, a maximum cell voltage of 3.3 V is achieved in case of PC:Pyr14TDI (1 : 3). However, despite the voltage limitation to 3 V, the highest specific energy and power values are obtained with the most diluted solution (3 : 1).

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Section: Introductionsupporting

confidence: 86%

“…It also offers better protection than TFSI À to corrosion of the aluminum current collector. [25,26] Given its melting point at ca. 48°C, [25] the use of pure Pyr14TDI as solvent-free electrolyte for EDLCs is excluded.…”

Section: Introductionmentioning

confidence: 99%

Electrolytes based on N‐Butyl‐N‐Methyl‐Pyrrolidinium 4,5‐Dicyano‐2‐(Trifluoromethyl) Imidazole for High Voltage Electrochemical Double Layer Capacitors

et al. 2018

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“…LiFSI, LiTFSI and LiDFOB), the LiTDI electrolyte exhibits a relatively high viscosity which contrasts with a previous report in EC:DMC (1:1) [48]. The high viscosity of the LiTDI electrolyte probably proceeds from the same reasons as the low density of the electrolytes, with a reduced mobility of species due to the presence of larger aggregates.…”

Section: Density Viscosity and Conductivitycontrasting

confidence: 53%

Towards practical sulfolane based electrolytes: Choice of Li salt for graphite electrode operation

Zhang

Porcher

Paillard

2018

Journal of Power Sources

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Abstract:Sulfolane (tetramethylene sulfone, SL) is known for leading to Li-ion electrolytes with high anodic stability. However, the operation of graphite electrodes in alternative electrolytes is usually challenging, especially when ethylene carbonate (EC) is not used as co-solvent. Thus, we study here the influence of the lithium salt on the physico-chemical and electrochemical properties of EC-free SL-based electrolytes and on the performance of graphite electrodes based on carboxymethyl cellulose (CMC). SL mixed with dimethyl carbonate (DMC) leads to electrolytes as conductive as state-of-theart alkyl carbonate-based electrolytes with wide electrochemical stability windows. The compatibility with graphite electrodes depends on the Li salt used and, even though cycling is possible with most salts, lithium difluoro-oxalato borate (LiDFOB) is especially interesting for graphite operation.LiDFOB electrolytes are conductive at room temperature (ca. 6 mS cm -1 ) with an anodic stability slightly below 5 V vs. Li/Li + on particulate carbon black electrodes. In addition, it allows cycling graphite electrodes with steady capacity and high coulombic efficiency without any additive. The testing of graphite electrodes in half-cells is, however, problematic with SL:DMC mixtures and, by switching the Li metal counter electrode for LiFePO4, the graphite electrode achieves better practical performance in terms of rate capability.

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“…Although the direct determination of the transference number introduced in the section Direct determination of the transference number by steady-state polarization experiments has initially been developed for polymer electrolytes, it is also often applied for liquid electrolytes, [28][29][30] ionic liquids 31 or mixtures of both, 32 even though it strictly is valid only for dilute solutions and cannot be applied to concentrated solutions due to a violation of the underlying assumptions as indicated in the section Direct determination of the transference number by steady-state polarization experiments. It is also shown that the experimental setup of the polarization cell with two lithium metal electrodes and the LiClO 4 electrolyte, as used in this contribution, is not suitable for low salt concentrations, since a constant electrolyte resistance cannot be guaranteed.…”

Section: Resultsmentioning

confidence: 99%

Determination of Transport Parameters in Liquid Binary Electrolytes: Part II. Transference Number

Ehrl

Landesfeind

Wall

et al. 2017

J. Electrochem. Soc.

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In the literature, various numerical methods for the simulation of ion-transport in concentrated binary electrolytes for lithium ion batteries can be found, whereas the corresponding transport parameters are rarely discussed. In this contribution, a novel method for the determination of the transference number in non-aqueous electrolytes is proposed. The method is based on data from a concentration cell and on the value of the thermodynamic factor obtained from independent measurements based on quantifying the redox potential of ferrocene. The concentration dependent transference numbers obtained by this new method are compared to values obtained by the classical approach, which is based on experiments in a polarization cell and a concentration cell. For the latter, a set of commonly used and some newly proposed analysis methods as well as their theoretical justification are discussed. Using an exemplary electrolyte (lithium perchlorate in a mixture of ethylene carbonate and diethyl carbonate), we will demonstrate that our newly proposed method based on concentration cell experiments and a thermodynamic factor derived from independent measurements is a more accurate approach for obtaining concentration dependent transference numbers. At the end, the experimentally determined concentration dependent transference numbers are compared to data available in the literature.

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LiTDI as electrolyte salt for Li-ion batteries: transport properties in EC/DMC

Cited by 57 publications

References 27 publications

Electrolytes based on N‐Butyl‐N‐Methyl‐Pyrrolidinium 4,5‐Dicyano‐2‐(Trifluoromethyl) Imidazole for High Voltage Electrochemical Double Layer Capacitors

Electrolytes based on N‐Butyl‐N‐Methyl‐Pyrrolidinium 4,5‐Dicyano‐2‐(Trifluoromethyl) Imidazole for High Voltage Electrochemical Double Layer Capacitors

Towards practical sulfolane based electrolytes: Choice of Li salt for graphite electrode operation

Determination of Transport Parameters in Liquid Binary Electrolytes: Part II. Transference Number

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