PROPERTIES AND STRUCTURES OF Li-N BASED HYDROGEN STORAGE MATERIALS

Traditional transportation fuel, petroleum, is limited and nonrenewable, and it also causes pollutions. Hydrogen is considered one of the best alternative fuels for transportation. The key issue for using hydrogen as fuel for transportation is hydrogen storage. Lithium nitride (Li3N) is an important material which can be used for hydrogen storage. The decompositions of lithium amide (LiNH2) and lithium imide (Li2NH) are important steps for hydrogen storage in Li3N. The effect of anions (e.g. Cl-) on the decomposition of LiNH2 has never been studied. Li3N can react with LiBr to form lithium nitride bromide Li13N4Br which has been proposed as solid electrolyte for batteries. The decompositions of LiNH2 and Li2NH with and without promoter were investigated by using temperature programmed decomposition (TPD) and X-ray diffraction (XRD) techniques. It was found that the decomposition of LiNH2 produced Li2NH and NH3 via two steps: LiNH2 into a stable intermediate species (Li1.5NH1.5) and then into Li2NH. The decomposition of Li2NH produced Li, N2 and H2 via two steps: Li2NH into an intermediate species --- Li4NH and then into Li. The kinetic analysis of Li2NH decomposition showed that the activation energies are 533.6 kJ/mol for the first step and 754.2 kJ/mol for the second step. Furthermore, XRD demonstrated that the Li4NH, which was generated in the decomposition of Li2NH, formed a solid solution with Li2NH. In the solid solution, Li4NH possesses a similar cubic structure as Li2NH. The lattice parameter of the cubic Li4NH is 0.5033nm. The decompositions of LiNH2 and Li2NH can be promoted by chloride ion (Cl-). The introduction of Cl- into LiNH2 resulted in the generation of a new NH3 peak at low temperature of 250 °C besides the original NH3 peak at 330 °C in TPD profiles. Furthermore, Cl- can decrease the decomposition temperature of Li2NH by about 110 °C. The degradation of Li3N was systematically investigated with techniques of XRD, Fourier transform infrared (FT-IR) spectroscopy, and UV-visible spectroscopy. It was found that O2 could not affect Li3N at room temperature. However, H2O in air can cause the degradation of Li3N due to the reaction between H2O and Li3N to LiOH. The produced LiOH can further react with CO2 in air to Li2CO3 at room temperature. Furthermore, it was revealed that Alfa-Li3N is more stable in air than Beta-Li3N. The chemical stability of Li13N4Br in air has been investigated by XRD, TPD-MS, and UV-vis absorption as a function of time. The aging process finally leads to the degradation of the Li13N4Br into Li2CO3, lithium bromite (LiBrO2) and the release of gaseous NH3. The reaction order n = 2.43 is the best fitting for the Li13N4Br degradation in air reaction. Li13N4Br energy gap was calculated to be 2.61 eV.

In Situ SHINERS at Electrochemical Single-Crystal Electrode/Electrolyte Interfaces: Tuning Preparation Strategies and Selected Applications

We have studied Au(55 nm)@SiO2 nanoparticles (NPs) on two low-index phases of gold and platinum single crystal electrodes in ClO4– and SO42– ion-containing electrolytes by both electrochemical methods and in-situ shell-isolated nanoparticle enhanced Raman spectroscopy (SHINERS). We showed the blocking of the electrode with surfactants originating from the synthesis of as-prepared SHINERS NPs. We introduce an efficient procedure to overcome this problem, which provides a fundamental platform for the application of SHINERS in surface electrochemistry and beyond. Our method is based on a hydrogen evolution treatment of the SHINERS-NP-modified single-crystal surfaces. The reliability of our preparation strategy is demonstrated in electrochemical SHINERS experiments on the potential-controlled adsorption and phase formation of pyridine on Au(hkl) and Pt(hkl). We obtained high-quality Raman spectra on these well-defined and structurally carefully characterized single-crystal surfaces. The analysis of the characteristic A1 vibrational modes revealed perfect agreement with the interpretation of single-crystal voltammetric and chronoamperometric experiments. Our study demonstrates that the SHINERS protocol developed in this work qualifies this Raman method as a pioneering approach with unique opportunities for in situ structure and reactivity studies at well-defined electrochemical solid/liquid interfaces.

Properties and applications of high electron density structures based on InN and related compounds

El objetivo principal del presente trabajo es estudiar y explotar estructuras que presentan un gas bidimensional de electrones (2DEG) basadas en compuestos nitruros con alto contenido de indio. Existen muchas preguntas abiertas, relacionadas con el nitruro de indio y sus aleaciones, algunas de las cuales se han abordado en este estudio. En particular, se han investigado temas relacionados con el análisis y la tecnología del material, tanto para el InN y heteroestructuras de InAl(Ga)N/GaN como para sus aplicaciones a dispositivos avanzados. Después de un análisis de la dependencia de las propiedades del InN con respecto a tratamientos de procesado de dispositivos (plasma y térmicos), el problema relacionado con la formación de un contacto rectificador es considerado. Concretamente, su dificultad es debida a la presencia de acumulación de electrones superficiales en la forma de un gas bidimensional de electrones, debido al pinning del nivel de Fermi. El uso de métodos electroquímicos, comparados con técnicas propias de la microelectrónica, ha ayudado para la realización de esta tarea. En particular, se ha conseguido lamodulación de la acumulación de electrones con éxito. En heteroestructuras como InAl(Ga)N/GaN, el gas bidimensional está presente en la intercara entre GaN y InAl(Ga)N, aunque no haya polarización externa (estructuras modo on). La tecnología relacionada con la fabricación de transistores de alta movilidad en modo off (E-mode) es investigada. Se utiliza un método de ataque húmedo mediante una solución de contenido alcalino, estudiando las modificaciones estructurales que sufre la barrera. En este sentido, la necesidad de un control preciso sobre el material atacado es fundamental para obtener una estructura recessed para aplicaciones a transistores, con densidad de defectos e inhomogeneidad mínimos. La dependencia de la velocidad de ataque de las propiedades de las muestras antes del tratamiento es observada y comentada. Se presentan también investigaciones relacionadas con las propiedades básicas del InN. Gracias al uso de una puerta a través de un electrolito, el desplazamiento de los picos obtenidos por espectroscopia Raman es correlacionado con una variación de la densidad de electrones superficiales. En lo que concierne la aplicación a dispositivos, debido al estado de la tecnología actual y a la calidad del material InN, todavía no apto para dispositivos, la tesis se enfoca a la aplicación de heteroestructuras de InAl(Ga)N/GaN. Gracias a las ventajas de una barrera muy fina, comparada con la tecnología de AlGaN/GaN, el uso de esta estructura es adecuado para aplicaciones que requieren una elevada sensibilidad, estando el canal 2DEG más cerca de la superficie. De hecho, la sensibilidad obtenida en sensores de pH es comparable al estado del arte en términos de variaciones de potencial superficial, y, debido al poco espesor de la barrera, la variación de la corriente con el pH puede ser medida sin necesidad de un electrodo de referencia externo. Además, estructuras fotoconductivas basadas en un gas bidimensional presentan alta ganancia debida al elevado campo eléctrico en la intercara, que induce una elevada fuerza de separación entre hueco y electrón generados por absorción de luz. El uso de metalizaciones de tipo Schottky (fotodiodos Schottky y metal-semiconductormetal) reduce la corriente de oscuridad, en comparación con los fotoconductores. Además, la barrera delgada aumenta la eficiencia de extracción de los portadores. En consecuencia, se obtiene ganancia en todos los dispositivos analizados basados en heteroestructuras de InAl(Ga)N/GaN. Aunque presentando fotoconductividad persistente (PPC), los dispositivos resultan más rápidos con respeto a los valores que se dan en la literatura acerca de PPC en sistemas fotoconductivos. ABSTRACT The main objective of the present work is to study and exploit the two-dimensionalelectron- gas (2DEG) structures based on In-related nitride compounds. Many open questions are analyzed. In particular, technology and material-related topics are the focus of interest regarding both InNmaterial and InAl(Ga)N/GaNheterostructures (HSs) as well as their application to advanced devices. After the analysis of the dependence of InN properties on processing treatments (plasma-based and thermal), the problemof electrical blocking behaviour is taken into consideration. In particular its difficulty is due to the presence of a surface electron accumulation (SEA) in the form of a 2DEG, due to Fermi level pinning. The use of electrochemical methods, compared to standard microelectronic techniques, helped in the successful realization of this task. In particular, reversible modulation of SEA is accomplished. In heterostructures such as InAl(Ga)N/GaN, the 2DEGis present at the interface between GaN and InAl(Ga)N even without an external bias (normally-on structures). The technology related to the fabrication of normally off (E-mode) high-electron-mobility transistors (HEMTs) is investigated in heterostructures. An alkali-based wet-etching method is analysed, standing out the structural modifications the barrier underwent. The need of a precise control of the etched material is crucial, in this sense, to obtain a recessed structure for HEMT application with the lowest defect density and inhomogeneity. The dependence of the etch rate on the as-grown properties is observed and commented. Fundamental investigation related to InNis presented, related to the physics of this degeneratematerial. With the help of electrolyte gating (EG), the shift in Raman peaks is correlated to a variation in surface eletron density. As far as the application to device is concerned, due to the actual state of the technology and material quality of InN, not suitable for working devices yet, the focus is directed to the applications of InAl(Ga)N/GaN HSs. Due to the advantages of a very thin barrier layer, compared to standard AlGaN/GaN technology, the use of this structure is suitable for high sensitivity applications being the 2DEG channel closer to the surface. In fact, pH sensitivity obtained is comparable to the state-of-the-art in terms of surface potential variations, and, due to the ultrathin barrier, the current variation with pH can be recorded with no need of the external reference electrode. Moreover, 2DEG photoconductive structures present a high photoconductive gain duemostly to the high electric field at the interface,and hence a high separation strength of photogenerated electron and hole. The use of Schottky metallizations (Schottky photodiode and metal-semiconductor-metal) reduce the dark current, compared to photoconduction, and the thin barrier helps to increase the extraction efficiency. Gain is obtained in all the device structures investigated. The devices, even if they present persistent photoconductivity (PPC), resulted faster than the standard PPC related decay values.

Quantum Dot-Sensitized Solar Cells Based on Directly Adsorbed Zinc Copper Indium Sulfide Colloids

Heavy metal-based quantum dots (QDs) have demonstrated to behave as efficient sensitizers in QD-sensitized solar cells (QDSSCs), as attested by the countless works and encouraging efficiencies reported so far. However, their intrinsic toxicity has arisen as a major issue for the prospects of commercialization. Here, we examine the potential of environmentally friendly zinc copper indium sulfide (ZCIS) QDs for the fabrication of liquid-junction QDSSCs by means of photoelectrochemical measurements. A straightforward approach to directly adsorb ZCIS QDs on TiO2 from a colloidal dispersion is presented. Incident photon-to-current efficiency (IPCE) spectra of sensitized photoanodes show a marked dependence on the adsorption time, with longer times leading to poorer performances. Cyclic voltammograms point to a blockage of the channels of the mesoporous TiO2 film by the agglomeration of QDs as the main reason for the decrease in efficiency. Photoanodes were also submitted to the ZnS treatment. Its effects on electron recombination with the electrolyte are analyzed through electrochemical impedance spectroscopy and photopotential measurements. The corresponding results bring out the role of the ZnS coating as a barrier layer preventing electron leakage toward the electrolyte, as argued in other QD-sensitized systems. The beneficial effect of the ZnS coating is ultimately reflected on the power conversion efficiency of complete devices, reaching values of 2 %. In a more general vein, through these findings, we aim to call the attention to the potentiality of this quaternary alloy, virtually unexplored as a light harvester for sensitized devices.

Asymmetric hybrid capacitors based on activated carbon and activated carbon fibre–PANI electrodes

Composites consisting of polyaniline (PANI) coatings inside the microporosity of an activated carbon fibre (ACF) were prepared by electrochemical and chemical methods. Electrochemical characterization of both composites points out that the electrodes with polyaniline show a higher capacitance than the pristine porous carbon electrode. These materials have been used to develop an asymmetric capacitor based on activated carbon (AC) as negative electrode and an ACF–PANI composite as positive electrode in H2SO4 solution as electrolyte. The presence of a thin layer of polyaniline inside the porosity of the activated carbon fibres avoids the oxidation of the carbon material and the oxygen evolution reaction is produced at more positive potentials. This capacitor was tested in a maximum cell voltage of 1.6 V and exhibited high energy densities, calculated for the unpackaged active materials, with values of 20 W h kg−1 and power densities of 2.1 kW kg−1 with excellent cycle lifetime (90% during the first 1000 cycles) and high coulombic efficiency.

Production of methanol from CO2 electroreduction at Cu2O and Cu2O/ZnO-based electrodes in aqueous solution

In this study, we examine the performance of Cu2O and Cu2O/ZnO surfaces in a filter-press electrochemical cell for the continuous electroreduction of CO2 into methanol. The electrodes are prepared by airbrushing the metal particles onto a porous carbon paper and then are electrochemically characterized by cyclic voltammetry analyses. Particular emphasis is placed on evaluating and comparing the methanol production and Faradaic efficiencies at different loadings of Cu2O particles (0.5, 1 and 1.8 mg cm−2), Cu2O/ZnO weight ratios (1:0.5, 1:1 and 1:2) and electrolyte flow rates (1, 2 and 3 ml min−1 cm−2). The electrodes including ZnO in their catalytic surface were stable after 5 h, in contrast with Cu2O-deposited carbon papers that present strong deactivation with time. The maximum methanol formation rate and Faradaic efficiency for Cu2O/ZnO (1:1)-based electrodes, at an applied potential of −1.3 V vs. Ag/AgCl, were r = 3.17 × 10−5 mol m−2 s−1 and FE = 17.7 %, respectively. Consequently, the use of Cu2O–ZnO mixtures may be of application for the continuous electrochemical formation of methanol, although further research is still required in order to develop highly active, selective and stable catalysts the electroreduction of CO2 to methanol.

The effect of carbon nanofillers on the performance of electromechanical polyaniline-based composite actuators

Different types of crystalline carbon nanomaterials were used to reinforce polyaniline for use in electromechanical bilayer bending actuators. The objective is to analyze how the different graphitic structures of the nanocarbons affect and improve the in situ polymerized polyaniline composites and their subsequent actuator behavior. The nanocarbons investigated were multiwalled carbon nanotubes, nitrogen-doped carbon nanotubes, helical-ribbon carbon nanofibers and graphene oxide, each one presenting different shape and structural characteristics. Films of nanocarbon-PAni composite were tested in a liquid electrolyte cell system. Experimental design was used to select the type of nanocarbon filler and composite loadings, and yielded a good balance of electromechanical properties. Raman spectroscopy suggests good interaction between PAni and the nanocarbon fillers. Electron microscopy showed that graphene oxide dispersed the best, followed by multiwall carbon nanotubes, while nitrogen-doped nanotube composites showed dispersion problems and thus poor performance. Multiwall carbon nanotube composite actuators showed the best performance based on the combination of bending angle, bending velocity and maximum working cycles, while graphene oxide attained similarly good performance due to its best dispersion. This parallel testing of a broad set of nanocarbon fillers on PAni-composite actuators is unprecedented to the best of our knowledge and shows that the type and properties of the carbon nanomaterial are critical to the performance of electromechanical devices with other conditions remaining equal.

Performance Assessment of a Polymer Electrolyte Membrane Electrochemical Reactor under Alkaline Conditions – A Case Study with the Electrooxidation of Alcohols

A novel polymer electrolyte membrane electrochemical reactor (PEMER) configuration has been employed for the direct electrooxidation of propargyl alcohol (PGA), a model primary alcohol, towards its carboxylic acid derivatives in alkaline medium. The PEMER configuration comprised of an anode and cathode based on nanoparticulate Ni and Pt electrocatalysts, respectively, supported on carbonaceous substrates. The electrooxidation of PGA was performed in 1.0 M NaOH, where a cathode based on a gas diffusion electrode was manufactured for the reduction of oxygen in alkaline conditions. The performance of a novel alkaline anion-exchange membrane based on Chitosan (CS) and Poly(vinyl) alcohol (PVA) in a 50:50 composition ratio doped with a 5 wt.% of poly (4-vinylpyridine) organic ionomer cross-linked, methyl chloride quaternary salt resin (4VP) was assessed as solid polymer electrolyte. The influence of 4VP anionic ionomer loading of 7, 12 and 20 wt.% incorporated into the electrocatalytic layers was examined by SEM and cyclic voltammetry (CV) upon the optimisation of the electroactive area, the mechanical stability and cohesion of the catalytic ink onto the carbonaceous substrate for both electrodes. The performance of the 4VP/CS:PVA membrane was compared with the commercial alkaline anion-exchange membrane FAA −a membrane generally used in direct alcohol alkaline fuel cells- in terms of polarisation plots in alkaline conditions. Furthermore, preparative electrolyses of the electrooxidation of PGA was performed under alkaline conditions of 1 M NaOH at constant current density of 20 mA cm−2 using a PEMER configuration to provide proof of the principle of the feasibility of the electrooxidation of other alcohols in alkaline media. PGA conversion to Z isomers of 3-(2-propynoxy)-2-propenoic acid (Z-PPA) was circa 0.77, with average current efficiency of 0.32. Alkaline stability of the membranes within the PEMER configuration was finally evaluated after the electrooxidation of PGA.

Comparative assessment of the gelatin particle agglutination test and an enzyme-linked immunosorbent assay for diagnosis of strongyloidiasis

The performances of the gelatin particle agglutination test (GPAT) and enzyme-linked immunosorbent assay (ELISA) for the diagnosis of strongyloidiasis with reference to the results of the agar plate culture technique (APCT) were evaluated with samples from 459 individuals from communities in northeast Thailand where strongyloidiasis is endemic. The prevalence of strongyloidiasis in five sample groups determined by GPAT varied between 29.3 and 61.5% (mean, 38.8%). ELISA and APCT, employed concurrently, gave lower prevalence rates of 27.5% (range, 21.6 to 42.1%) and 22.7% (range, 12.7 to 53.8%), respectively. By using APCT as the standard method, the sensitivity of GPAT was generally higher than that of ELISA (81 versus 73%). The specificity of GPAT was slightly lower than that of ELISA (74 versus 86%). The resulting GPAT titers exhibited positive linear relationships with the ELISA values (optical density at 490 nm) (P < 0.05), which suggests that the GPAT titer also reflects the levels of specific antibody comparable to those reflected by the ELISA values. Based on the relative ease and simplicity of use of the technique as well as the acceptable rates of sensitivity and specificity of the test, GPAT is more practical for screening for strongyloidiasis than the conventional ELISA.

Operation of polymer electrolyte membrane fuel cells with dry feeds: Design and operating strategies

The operation of polymer electrolyte membrane fuel cells (PEMFCs) with dry feeds has been examined with different fuel cell flow channel designs as functions of pressure, temperature and flow rate. Auto-humidified (or self-humidifying) PEMFC operation is improved at higher pressures and low gas velocities where axial dispersion enhances back-mixing of the product water with the dry feed. We demonstrate auto-humidified operation of the channel-less, self-draining fuel cell, based on a stirred tank reactor; data is presented showing auto-humidified operation from 25 to 115 degrees C at 1 and 3 atm. Design and operating requirements are derived for the auto-humidified operation of the channel-less, self-draining fuel cell. The auto-humidified self-draining fuel cell outperforms a fully humidified serpentine flow channel fuel cell at high current densities. The new design offers substantial benefits for simplicity of operation and control including: the ability to self-drain reducing flooding, the ability to uniformly disperse water removing current gradients and the ability to operate on dry feeds eliminating the need for humidifiers. Additionally, the design lends itself well to a modular design concept. (c) 2005 Elsevier B.V. All rights reserved.

Adipose tissue engineering based on the controlled release of fibroblast growth factor-2 in a collagen matrix

Adipose tissue forms when basement membrane extract ( Matrigel (TM)) and fibroblast growth factor-2 (FGF-2) are added to our mouse tissue engineering chamber model. A mouse tumor extract, Matrigel is unsuitable for human clinical application, and finding an alternative to Matrigel is essential. In this study we generated adipose tissue in the chamber model without using Matrigel by controlled release of FGF-2 in a type I collagen matrix. FGF-2 was impregnated into biodegradable gelatin microspheres for its slow release. The chambers were filled with these microspheres suspended in 60 mu L collagen gel. Injection of collagen containing free FGF-2 or collagen containing gelatin microspheres with buffer alone served as controls. When chambers were harvested 6 weeks after implantation, the volume and weight of the tissue obtained were higher in the group that received collagen and FGF-2 impregnated microspheres than in controls. Histologic analysis of tissue constructs showed the formation of de novo adipose tissue accompanied by angiogenesis. In contrast, control groups did not show extensive adipose tissue formation. In conclusion, this study has shown that de novo formation of adipose tissue can be achieved through controlled release of FGF-2 in collagen type I in the absence of Matrigel.

Tissue engineering of co-cultured skin substitutes using biocomposite membranes based on collagen and polycaprolactone

The preparation and characterisation of collagen: PCL, gelatin: PCL and gelatin/collagen:PCL biocomposites for manufacture of tissue engineered skin substitutes are reported. Films of collagen: PLC, gelatin: PCL (1:4, 1:8 and 1:20 w/w) and gelatin/collagen:PCL (1:8 and 1:20 w/w) biocomposites were prepared by impregnation of lyophilised collagen and/or gelatin mats by PCL solutions followed by solvent evaporation. In vitro assays of total protein release of collagen:PCL and gelatin: PCL biocomposite films revealed an expected inverse relationship between the collagen release rate and the content of synthetic polymer in the biocomposite samples that may be exploited for controlled presentation and release of biopharmaceuticals such as growth factors. Good compatibility of all biocomposite groups was proven by interaction with 3T3 fibroblasts, normal human epidermal keratinocytes (NHEK), and primary human epidermal keratinocytes (PHEK) and dermal fibroblasts (PHDF) in vitro respectively. The 1:20 collagen: PCL materials exhibiting good cell growth curves and mechanical characteristics were selected for engineering of skin substitutes in this work. The tissue-engineered skin model based on single-donor PHEK and PHDF with differentiated confluent epidermal layer and fibrous porous dermal layer was then developed successfully in vitro proven by SEM and immunohistochemistry assay. The following in vivo animal study on athymic mice revealed early complete wound healing in 10 days and good integration of co-cultured skin substitutes with adjacent mice skin structures. Thus the co-cultured skin substitutes based on 1:20 collagen: PCL biocomposite membranes was proven in principle. The approach to skin modelling reported here may find application in wound treatment, gene therapy and screening of new pharmaceuticals.

Synthesis and characterization of nanocomposites based on PANI and carbon nanostructures prepared by electropolymerization

Nanocomposites based on polyaniline (PANI) and carbon nanostructures (CNSs) (graphene (G) and multiwall carbon nanotubes (MWCNTs)) were prepared by in situ electrochemical polymerization. CNSs were inserted into the PANI matrix by dispersing them into the electrolyte before the electropolymerization. Electrochemical characterization by means of cyclic voltammetry and steady state polarization were performed in order to determine conditions for electro- polymerization. Electro-polymerization of the PANI based nanocomposites was carried out at 0.75 V vs. saturated calomel electrode (SCE) for 40 and 60 minutes. The morphology and structural characteristics of the obtained nanocomposites were studied by scanning electron microscopy (SEM) and Raman spectroscopy, while thermal stability was determined using thermal gravimetric analysis (TGA). According to the morphological and structural study, fibrous and porous structure of PANI based nanocomposites was detected well embedding both G and MWCNTs. Also, strong interaction between quinoidal structure of PANI with carbon nanostructures via π–π stacking was detected by Raman spectroscopy. TGA showed the increased thermal stability of composites reinforced with CNSs, especially those reinforced with graphene.

Effect of the Electrolyte Formulation on the Performances of Edlc and Li-Ion Batteries

One of the most important components in electrochemical storage devices (batteries and supercapacitors) is undoubtedly the electrolyte. The basic function of any electrolyte in these systems is the transport of ions between the positive and negative electrodes. In addition, electrochemical reactions occurring at each electrode/electrolyte interface are the origin of the current generated by storage devices. In other words, performances (capacity, power, efficiency and energy) of electrochemical storage devices are strongly related to the electrolyte properties, as well as, to the affinity for the electrolyte to selected electrode materials. Indeed, the formulation of electrolyte presenting good properties, such as high ionic conductivity and low viscosity, is then required to enhance the charge transfer reaction at electrode/electrolyte interface (e.g. charge accumulation in the case of Electrochemical Double Layer Capacitor, EDLC). For practical and safety considerations, the formulation of novel electrolytes presenting a low vapor pressure, a large liquid range temperature, a good thermal and chemical stabilities is also required.

This lecture will be focused on the effect of the electrolyte formulation on the performances of electrochemical storage devices (Li-ion batteries and supercapacitors). During which, a summary of the physical, thermal and electrochemical data obtained by our group, recently, on the formulation of novel electrolyte-based on the mixture of an ionic liquid (such as EmimNTf2 and Pyr14NTf2) and carbonate or dinitrile solvents will be presented and commented. The impact of the electrolyte formulation on the storage performances of EDLC and Li-ion batteries will be also discussed to further understand the relationship between electrolyte formulation and electrochemical performances. This talk will also be an opportunity to further discuss around the effects of additives (SEI builder: fluoroethylene carbonate and vinylene carbonate), ionic liquids, structure and nature of lithium salt (LiTFSI vs LiPF6) on the cyclability of negative electrode to then enhance the electrolyte formulation. For that, our recent results on TiSnSb and graphite negative electrodes will be presented and discussed, for example 1,2.

1-C. Marino, A. Darwiche1, N. Dupré, H.A. Wilhelm, B. Lestriez, H. Martinez, R. Dedryvère, W. Zhang, F. Ghamouss, D. Lemordant, L. Monconduit “ Study of the Electrode/Electrolyte Interface on Cycling of a Conversion Type Electrode Material in Li Batteries” J. Phys.chem. C, 2013, 117, 19302-19313

2- Mouad Dahbi, Fouad Ghamouss, Mérièm Anouti, Daniel Lemordant, François Tran-Van “Electrochemical lithiation and compatibility of graphite anode using glutaronitrile/dimethyl carbonate mixtures containing LiTFSI as electrolyte” 2013, 43, 4, 375-385.

The use of binary mixtures of 1-butyl-1-methylpyrrolidinium bis{(trifluoromethyl)sulfonyl}imide and aliphatic nitrile solvents as electrolyte for supercapacitors

Abstract The development of high voltage electrolytes is one of the key aspects for increasing both energy and power density of electrochemical double layer capacitors (EDLCs). The usage of blends of ionic liquids and organic solvents has been considered as a feasible strategy since these electrolytes combine high usable voltages and good transport properties at the same time. In this work, the ionic liquid 1-butyl-1-methylpyrrolidinium bis{(trifluoromethyl)sulfonyl}imide ([Pyrr14][TFSI]) was mixed with two nitrile-based organic solvents, namely butyronitrile and adiponitrile, and the resulting blends were investigated regarding their usage in electrochemical double layer capacitors. Both blends have a high electrochemical stability, which was confirmed by prolonged float tests at 3.2 V, as well as, good transport properties. In fact, the butyronitrile blend reaches a conductivity of 17.14 mS·cm−1 and a viscosity of 2.46 mPa·s at 20 °C, which is better than the state-of-the-art electrolyte (1 mol·dm−3 of tetraethylammonium tetrafluoroborate in propylene carbonate).