Elie Paillard

Electrochemical and Physicochemical Properties of PY14FSI -Based Electrolytes with LiFSI

We report here the characterization of Li battery electrolytes based upon the N-butyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide ionic liquid (PY 14 FSI) with lithium bis(fluorosulfonyl)imide (LiFSI) as a support salt. These electrolytes show low viscosity relative to other pyrrolidinium-based ionic liquids (ILs) and corresponding higher conductivity at subambient temperatures. The melting point of the IL decreases with the addition of LiFSI and concentrated samples remain totally amorphous. The electrolytes exhibit decreased thermal stability and increased parasitic cathodic reactions with increasing LiFSI fraction relative to the pure IL, probably due to a higher impurity level for the commercial LiFSI. Despite this, the electrolytes have excellent lithium cycling behavior at 20°C.

Homogeneous Lithium Electrodeposition with Pyrrolidinium-Based Ionic Liquid Electrolytes

In this study, we report on the electroplating and stripping of lithium in two ionic liquid (IL) based electrolytes, namely N-butyl-N-methylpyrrolidinium bis(fluorosulfonyl) imide (Pyr14FSI) and N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (Pyr14TFSI), and mixtures thereof, both on nickel and lithium electrodes. An improved method to evaluate the Li cycling efficiency confirmed that homogeneous electroplating (and stripping) of Li is possible with TFSI-based ILs. Moreover, the presence of native surface features on lithium, directly observable via scanning electron microscope imaging, was used to demonstrate the enhanced electrolyte interphase (SEI)-forming ability, that is, fast cathodic reactivity of this class of electrolytes and the suppressed dendrite growth. Finally, the induced inhomogeneous deposition enabled us to witness the SEI cracking and revealed previously unreported bundled Li fibers below the pre-existing SEI and nonrod-shaped protuberances resulting from Li extrusion.

Ionic Liquid Electrolytes for Li–Air Batteries: Lithium Metal Cycling

In this work, the electrochemical stability and lithium plating/stripping performance of N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (Pyr14TFSI) are reported, by investigating the behavior of Li metal electrodes in symmetrical Li/electrolyte/Li cells. Electrochemical impedance spectroscopy measurements and galvanostatic cycling at different temperatures are performed to analyze the influence of temperature on the stabilization of the solid electrolyte interphase (SEI), showing that TFSI-based ionic liquids (ILs) rank among the best candidates for long-lasting Li–air cells.

Challenges of “Going Nano”: Enhanced Electrochemical Performance of Cobalt Oxide Nanoparticles by Carbothermal Reduction and In Situ Carbon Coating

The electrochemical performance of nano- and micron-sized Co(3)O(4) is investigated, highlighting the substantial influence of the specific surface area on the obtainable specific capacities as well as the cycling stability. In fact, Co(3)O(4) materials with a high surface area (i.e. a small particle size) show superior specific features, which are, however, accompanied by a rapid capacity fading, owing to the increased formation of an insulating polymeric surface film that results from transition-metal-catalyzed electrolyte decomposition. The simultaneous coating with carbon of Co(3)O(4) nanoparticles and in situ reduction of the Co(3)O(4) by a carbothermal route yields a CoO-Co-C nanocomposite. The formation of this material substantially enhances the long-term cycling stability and coulombic efficiency of the lithium-ion active material used. Although the metallic cobalt enhances the electronic conductivity within the electrode and remains electrochemically inactive (as revealed by in situ powder X-ray diffraction analysis), it might have a detrimental effect on the long-term cycling stability by catalytically inducing continuous electrolyte decomposition.

A joint theoretical/experimental study of the structure, dynamics, and Li+ transport in bis([tri]fluoro[methane]sulfonyl)imide [T]FSI-based ionic liquids.

The structure and dynamics of N-butyl-N-methyl pyrrolidinium(+) bis([tri]fluoro[methane]sulfonyl)imide(-) (PYR14(+)-[T]FSI(-)) ionic liquids doped with Li(T)FSI are investigated by combining experimental measurements to molecular dynamics simulations. The polarizable force field calculations indicate that the lithium cations are coordinated by (T)FSI anion oxygens forming lithium adducts stabilized over a large temperature range by strong Li-O bonds. Lithium aggregation is found to be negligible at the doping level considered here (10% mole fraction), and Li(+) diffusion occurs primarily by exchanging the (T)FSI anions in their first coordination shell. The resulting calculated transport properties are in good agreement with the corresponding nuclear magnetic resonance data.

Ionic Liquid-based Electrolytes for Li Metal/Air Batteries: A Review of Materials and the New 'LABOHR' Flow Cell Concept

The Li-O2 battery has been attracting much attention recently, due to its very high theoretical capacity compared with Li-ion chemistries. Nevertheless, several studies within the last few years revealed that Li-ion derived electrolytes based on alkyl carbonate solvents, which have been commonly used in the last 27 years, are irreversibly consumed at the O2 electrode. Accordingly, more stable electrolytes are required capable to operate with both the Li metal anode and the O2 cathode. Thus, due to their favorable properties such as non volatility, chemical inertia, and favorable behavior toward the Li metal electrode, ionic liquid-based electrolytes have gathered increasing attention from the scientific community for its application in Li-O2 batteries. However, the scale-up of Li-O2 technology to real application requires solving the mass transport limitation, especially for supplying oxygen to the cathode. Hence, the ‘LABOHR’ project proposes the introduction of a flooded cathode configuration and the circulation of the electrolyte, which is then used as an oxygen carrier from an external O2 harvesting device to the cathode for freeing the system from diffusion limitation.

Separators for Li-Ion and Li-Metal Battery Including Ionic Liquid Based Electrolytes Based on the TFSI⁻ and FSI⁻ Anions

The characterization of separators for Li-ion or Li-metal batteries incorporating hydrophobic ionic liquid electrolytes is reported herein. Ionic liquids made of N-butyl-N-methylpyrrolidinium (PYR14+) or N-methoxyethyl-N-methylpyrrolidinium (PYR12O1+), paired with bis(trifluoromethanesulfonyl)imide (TFSI−) or bis(fluorosulfonyl)imide (FSI−) anions, were tested in combination with separators having different chemistries and morphologies in terms of wetting behavior, Gurley and McMullin number, as well as Li/(Separator + Electrolyte) interfacial properties. It is shown that non-functionalized microporous polyolefin separators are poorly wetted by FSI−-based electrolytes (contrary to TFSI−-based electrolytes), while the ceramic coated separator Separion® allows good wetting with all electrolytes. Furthermore, by comparing the lithium solid electrolyte interphase (SEI) resistance evolution at open circuit and during cycling, depending on separator morphologies and chemistries, it is possible to propose a scale for SEI forming properties in the order: PYR12O1FSI > PYR14FSI > PYR14TFSI > PYR12O1TFSI. Finally, the impact the separator morphology is evidenced by the SEI resistance evolution and by comparing Li electrodes cycled using separators with two different morphologies.

A 3D porous Li-rich cathode material with an in situ modified surface for high performance lithium ion batteries with reduced voltage decay

High crystallinity Li-rich porous materials integrated with an in situ formed surface containing carbonaceous compounds are synthesized through a facile approach. The rationally designed procedure involves the formation of a specific morphology of a hydroxide precursor assisted by a self-made template and subsequent high temperature treatment to obtain a Li1.2Mn0.56Ni0.16Co0.08O2 target product. The porous morphology is investigated using field-emission scanning electron microscopy and its surface area is quantitatively examined by gas sorption analysis coupled with the Brunauer–Emmett–Teller method. The crystallinity is characterized by X-ray diffraction and high-resolution transmission electron microscopy. X-ray photoelectron spectroscopy, CHN elemental analysis and small angle neutron scattering confirm the presence of carbonaceous compounds in the surface composition. The prepared material exhibits superior discharge rate capability and excellent cycling stability. It shows minor capacity loss after 100 cycles at 0.5C and retains 94.9% of its initial capacity after 500 cycles at 2C. Even more notably, the “voltage decay” during cycling is also significantly decreased. It has been found that carbonaceous compounds play a critical role in reducing the layered to spinel structural transformation during cycling. Therefore, the present porous Li-rich material with surface modified carbonaceous compounds represents an attractive material for advanced lithium-ion batteries.

Aerosol-gel deposition of photocurable ORMOSIL films doped with a terbium complex

Abstract Photocurable SiO 2 –TiO 2 ORMOSIL films have been deposited using the aerosol–gel process. 3-(trimethoxysilyl) propylmethacrylate and tetraisopropyl-orthotitanate complexed with methacrylic acid were used as sol–gel precursors. Doping with a terbium:sulphosalicylic acid complex was also studied to test the deposition of optically active photocurable films. Photopolymerization and photoluminescence properties of the films are reported. The results demonstrate the potential of UV-writing of aerosol–gel deposited active thin films.

Lithium-ion batteries (LIBs) for medium- and large-scale energy storage:: current cell materials and components

This chapter offers a brief overview on state-of-the-art active anode and cathode and inactive electrolyte, separator, binder, and current collector materials currently used in commercial lithium-ion batteries (LIBs). Their major advantages are highlighted, which explain why LIBs are presently the leading battery technology. In addition, their major limitations with respect to future large-scale applications in electric vehicles and/or stationary energy storage devices are also reviewed.