Non-Flammable Sodium Asymmetric Imide Salt-Based Deep Eutectic Solvent for Supercapacitor Applications.

This study reports two deep eutectic solvents (DESs) based on alkaline imide salts with asymmetric anions as functional electrolytes for supercapacitor (SC) application. The eutectic mixture of sodium (fluorosulfonyl) (trifluoromethanesulfonyl) imide (NaFTFSI) or sodium cyano-trifluoromethanesulfonyl imide (NaTFSICN) with ethylene carbonate (EC) delivers a non-flammable and stable liquid. The eutectic diagrams of the electrolytes directed to an optimal composition (wsalt =0.25), hinging to that of conventional carbonate-based electrolytes, i. e., 1 mol L-1 . The volumetric properties of the DESs revealed a "stacking" effect, reflecting a strong coordination bond between the imide and EC anions without solvating the Na+ cations. The DES transport properties (i. e., viscosity, conductivity, and ionicity) and temperature variations designate a high organization, similar to ionic liquids. The DESs, when coupled with activated carbon electrodes in a two-electrode symmetric configuration, yield specific capacities of 150 F g-1 at a normalized current density of 0.5 A g-1 (and 120 F g-1 at 2 A g-1 ). The SC maintained 80 % of its initial capacity beyond 100 h of floating at an operating voltage of 2.4 V and showed a 150 mV per hour potential loss under self-discharge. The devised eutectic mixtures offer a promising new pathway for simple, safe, and effective electrolytes for SC applications.

Role of FTFSI Anion Asymmetry on Physical Properties of AFTFSI (A=Li, Na and K) Based Electrolytes and Consequences on Supercapacitor Application.

This study compares the physicochemical properties of six electrolytes comprising of three salts: LiFTFSI, NaFTFSI and KFTFSI in two solvent mixtures, the binary (3EC/7EMC) and the ternary (EC/PC/3DMC). The transport properties (conductivity, viscosity) as a function of temperature and concentration were modeled using the extended Jones-Dole-Kaminsky equation, the Arrhenius model, and the Eyring theory of transition state for activated complexes. Results are discussed in terms of ionicity, solvation shell, and cross-interactions between electrolyte components. The application of the six formulated electrolytes in symmetrical activated carbon (AC)//AC supercapacitors (SCs) was characterized by cyclic voltammetry (CV), galvanostatic cycling with potential limitation (GCPL), electrochemical impedance spectroscopy (EIS) and accelerated aging. Results revealed that the geometrical flexibility of the FTFSI anion allows it to access and diffuse easily in AC whereas its counter ions (Li+ , Na+ or K+ ) can remain trapped in porosity. However, this drawback was partially resolved by mixing LiFTFSI and KFTFSI salts in the electrolyte.

Amide-based deep eutectic solvents containing LiFSI and NaFSI salts as superionic electrolytes for supercapacitor applications.

This work proposes two deep eutectic solvents (DESs) based on lithium bis(fluorosulfonyl)imide and sodium bis(fluorosulfonyl)imide together with N-methylacetamide and formamide as electrolytes for activated carbon (AC) electrochemical double-layer capacitors (EDLCs) at 25 °C. The formulated DESs exhibit a large electrochemical window (ΔE > 2.5 V), good thermal stability (∼150 °C) and ionic conductivity (3-4 mS cm-1), and moderate viscosity (11.3 mPa s). Through the Vogel-Tamman-Vulcher fitting equation, the evolution of pseudo-energy activation was delineated with respect to the nature of the H-bond donor or alkali salt. These electrolytes present a superionic character gleaned from the Walden classification, and their ionicity exceeds that of standard organic electrolytes based on similar alkali salts. The performance of the AC-based EDLC was assessed by cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic charge/discharge, yielding 140 F g-1 with an 8% capacity retention during 200 h of floating. Based on the physicochemical properties and electrochemical performance of these DESs, they represent a promising green-alternative electrolyte for supercapacitor applications.

Comparative Study of Alkali-Cation-Based (Li+ , Na+ , K+ ) Electrolytes in Acetonitrile and Alkylcarbonates.

The development of a suitable functional electrolyte is urgently required for fast-charging and high-voltage alkali-ion (Li, Na, K) batteries as well as next-generation hybrids supercapacitors. Many recent works focused on an optimal selection of electrolytes for alkali-ion based systems and their electrochemical performance but the understanding of the fundamental aspect that explains their different behaviour is rare. Herein, we report a comparative study of transport properties for LiPF6 , NaPF6 , KPF6 in acetonitrile (AN) and a binary mixture of ethylene carbonate (EC), dimethyl carbonate (DMC): (EC/DMC : 1/1, weigh) through conductivities, densities and viscosities measurements in wide temperature domain. By application of the Stokes-Einstein, Nernst-Einstein, and Jones Dole equations, the effective ionic solvated radius of cation (reff ), the ionic dissociation coefficient (αD ) and structuring Jones Dole's parameters (A, B) for salt are calculated and discussed according to solvent or cation nature as a function of temperature. From the results, we demonstrate that better mobility of potassium can be explained by the nature of the ion-ion and ion-solvent interactions due to its polarizability. In the same time, the predominance of triple ions in the case of K+ , is a disadvantage at high concentration.

Ionic association analysis of LiTDI, LiFSI and LiPF6 in EC/DMC for better Li-ion battery performances.

New lithium salts such as lithium bis(fluorosulfonyl)imide (LiFSI) and lithium 4,5-dicyano-2-(trifluoromethyl)imidazole-1-ide (LiTDI) are now challenging lithium hexafluorophosphate (LiPF6), the most used electrolyte salt in commercial Li-ion batteries. Thus it is now important to establish a comparison of these electrolyte components in a standard solvent mixture of ethylene carbonate and dimethyl carbonate (EC/DMC: 50/50 wt%). With this aim, transport properties, such as the ionic conductivity, viscosity and 7Li self-diffusion coefficient have been deeply investigated. Moreover, as these properties are directly linked to the nature of the interionic interactions and ion solvation, a better understanding of the structural properties of electrolytes can be obtained. The Li salt concentration has been varied over the range of 0.1 mol L-1 to 2 mol L-1 at 25 °C and the working temperature from 20 °C to 80 °C at the fixed concentration of 1 mol L-1. Experimental results were used to investigate the temperature dependence of the salt ion-pair (IP) dissociation coefficient (α D) with the help of the Walden rule and the Nernst-Einstein equation. The lithium cation effective solute radius (r Li) has been determined using the Jones-Dole-Kaminsky equation coupled to the Einstein relation for the viscosity of hard spheres in solution and the Stokes-Einstein equation. From the variations of α D and rLi with the temperature, it is inferred that in EC/DMC LiFSI forms solvent-shared ion-pairs (SIP) and that, LiTDI and LiPF6 are likely to form solvent separated ion-pairs (S2IP) or a mixture of SIP and S2IP. From the temperature dependence of α D, thermodynamic parameters such as the standard Gibbs free energy, enthalpy and entropy for the ion-pair formation are obtained. Besides being in agreement with the information provided by the variations of α D and rLi, it is concluded that the ion-pair formation process is exergonic and endothermic for the three salts in EC/DMC.

Synthesis and Thermophysical Properties of Ether-Functionalized Sulfonium Ionic Liquids as Potential Electrolytes for Electrochemical Applications.

During this work, a novel series of hydrophobic room temperature ionic liquids (ILs) based on five ether functionalized sulfonium cations bearing the bis{(trifluoromethyl)sulfonyl}imide, [NTf2 ]- anion were synthesized and characterized. Their physicochemical properties, such as density, viscosity and ionic conductivity, electrochemical window, along with thermal properties including phase transition behavior and decomposition temperature, have been measured. All of these ILs showed large liquid range temperature, low viscosity, and good conductivity. Additionally, by combining DFT calculations along with electrochemical characterization it appears that these novel ILs show good electrochemical stability windows, suitable for the potential application as electrolyte materials in electrochemical energy storage devices.

A pyrrolidinium nitrate protic ionic liquid-based electrolyte for very low-temperature electrical double-layer capacitors.

This study describes the use of the pyrrolidinium nitrate ([Pyrr][NO3]) protic ionic liquid (PIL) in a mixture with gamma butyrolactone (γ-BL) as an electrolyte for carbon-based supercapacitors with an operating voltage of 2.0 V and at very low temperature. Thermal and transport properties of this electrolyte were firstly evaluated from -40 °C to 80 °C. The evolution of conductivity with the addition of γ-BL rendered it possible to determine the optimal composition for electrochemical application, with a molar fraction of γ-BL of 0.6. This mixture shows a Newtonian behavior with a low viscosity value of 5 mPa s at 25 °C, and exhibits high conductivity values of up to 65 mS cm(-1) at 80 °C. At the same time, exceptional residual conductivity was measured for this composition at -40 °C (9 mS cm(-1)), thanks to the superionic character of pyrrolidinium nitrate PIL. Electrochemical characterization of this electrolyte demonstrated, at first, a passivation on the aluminum collector, secondly good cycling performances with an activated carbon electrode from 50 °C to -40 °C with capacitance up to 132 F g(-1) at room temperature and a wide voltage window (2.0 V). Finally at very low temperature (-40 °C), this system demonstrates an unprecedented combination of high specific capacitance (up to 117 F g(-1)), and rapid charging-discharging even at high current density, which is very promising for the progress of energy storage systems with environmentally friendly electrolytes at such very low temperatures.

Triethylammonium bis(tetrafluoromethylsulfonyl)amide protic ionic liquid as an electrolyte for electrical double-layer capacitors.

This study describes the preparation, characterization and application of [Et(3)NH][TFSA], either neat or mixed with acetonitrile, as an electrolyte for supercapacitors. Thermal and transport properties were evaluated for the neat [Et(3)NH][TFSA], and the temperature dependence of viscosity and conductivity can be described by the VTF equation. The evolution of conductivity with the addition of acetonitrile rendered it possible to determine the optimal mixture at 25 °C, with a weight fraction of acetonitrile of 0.5. This mixture was also evaluated for transport properties, and showed a Newtonian behavior, as the neat PIL. An electrochemical study demonstrated, at first, a passivation on Al after the second cyclic voltammogram. Subsequently, the electrochemical window was estimated using a three-electrode cell to 4 V on a platinum electrode, and to 2.5 V on activated carbon. Finally, the neat PIL was found to exhibit good performances as promising electrolyte for supercapacitor applications.