Silicon-Based Composite Anodes for All-Solid-State Lithium-Ion Batteries Conceived by a Mixture Design Approach.

Silicon-based anodes composed of micrometric Si, graphite (MAG), LiI-Li3 PS4 solid electrolyte (LPSI), and carbon nanofiber (CNF), which can be prepared by straightforward manual grinding, are proposed in this study. The relation between composition and performance of the anodes is investigated through the mixture design approach, which allows discrimination of the effect of each component and also the combined effect of the components on the end performance. By increasing the fraction of LPSI in the anode, the capacity of the electrode is improved, and the best performance is obtained when the Si/MAG/LPSI ratio is 15 : 15 : 70. This composite integrated with 5 wt % CNF exhibits a capacity above 1200 mAh g-1 throughout 50 cycles in a bulk-type all-solid-state battery with LPSI as the electrolyte. Scanning electron microscopy (SEM) confirms that the presence of LPSI suppresses the aggregation of Si and improves the ratio of Si available for lithiation/delithiation.

Novel MIPs-Parabens based SPE Stationary Phases Characterization and Application.

In this work, the synthesis, characterization, and application of novel parabens imprinted polymers as highly selective solid-phase extraction (SPE) sorbents have been reported. The imprinted polymers were created using sol-gel molecular imprinting process. All the seven parabens were considered herein in order to check the phase selectivity. By means of a validated HPLC-photodiode array detector (PDA) method all seven parabens were resolved in a single chromatographic run of 25 min. These SPE sorbents, in-house packed in SPE empty cartridges, were first characterized in terms of extraction capability, breakthrough volume, retention volume, hold-up volume, number of theoretical plates, and retention factor. Finally, the device was applied to a real urine sample to check the method feasibility on a very complex matrix. The new paraben imprinted SPE sorbents, not yet present in the literature, potentially encourage the development of novel molecularly imprinted polymers (MIPs) to enhance the extraction efficiency, and consequently the overall analytical performances, when the trace quantification is required.

Electrospun Carbon/Cu x O Nanocomposite material as Sustainable and High Performance Anode for Lithium-Ion Batteries.

The increase in energy density of the next generation of battery materials to meet the new challenges of the electrical vehicles era calls for innovative and easily scalable materials with sustainable processes. An innovative Cu x O/C nanocomposite material, characterized by a highly conductive 3D-framework, with Cu x O/Cu-metal contiguous nanodomains is prepared by electrospinning. The electrode processing is made using a polyacrylic acid binder. The nanocomposite has been fully characterized and the electrochemical performance shows high specific capacity values over 450 galvanostatic cycles at 500 mAg-1 specific current with capacity retention values over 80 %. In addition, the composite shows remarkable high rate performance and highly stable interface, which has been studied by impedance spectroscopy.

Comparison between Exhaustive and Equilibrium Extraction Using Different SPE Sorbents and Sol-Gel Carbowax 20M Coated FPSE Media.

This paper reports the performance comparison between the exhaustive and equilibrium extraction using classical Avantor C18 solid phase extraction (SPE) sorbent, hydrophilic-lipophilic balance (HLB) SPE sorbent, Sep-Pak C18 SPE sorbent, novel sol-gel Carbowax 20M (sol-gel CW 20M) SPE sorbent, and sol-gel CW 20M coated fabric phase sorptive extraction (FPSE) media for the simultaneous extraction and analysis of three inflammatory bowel disease (IBD) drugs that possess logP values (polarity) ranging from 1.66 for cortisone, 2.30 for ciprofloxacin, and 2.92 for sulfasalazine. Both the commercial SPE phases and in-house synthesized sol-gel CW 20M SPE phases were loaded in SPE cartridges and the extractions were carried out under an exhaustive extraction mode. FPSE was carried out under an equilibrium extraction mode. The drug compounds were resolved using a Luna C18 column (250 mm × 4.6 mm; 5 m particle size) in gradient elution mode within 20 min and the method was validated in compliance with international guidelines for the bioanalytical method validation. Novel in-house synthesized and loaded sol-gel CW 20M SPE sorbent cartridges were characterized in terms of their extraction capability, breakthrough volume, retention volume, hold-up volume, number of the theoretical plate, and the retention factor.

Gel Polymer Electrolytes Based on Silica-Added Poly(ethylene oxide) Electrospun Membranes for Lithium Batteries.

Solid polymer electrolytes, in the form of membranes, offering high chemical and mechanical stability, while maintaining good ionic conductivity, are envisaged as a possible solution to improve performances and safety in different lithium cell configurations. In this work, we designed and prepared systems formed using innovative nanocomposite polymer membranes, based on high molecular weight poly(ethylene oxide) (PEO) and silica nanopowders, produced by the electrospinning technique. These membranes were subsequently gelled with solutions based on aprotic ionic liquid, carbonate solvents, and lithium salt. The addition of polysulfide species to the electrolyte solution was also considered, in view of potential applications in lithium-sulfur cells. The morphology of the electrospun pristine membranes was evaluated using scanning electron microscopy. Stability and thermal properties of pristine and gelled systems were investigated uisng differential scanning calorimetry and thermal gravimetric analysis. Electrochemical impedance spectroscopy was used to determine the conductivity of both swelling solutions and gelled membranes, allowing insight into the ion transport mechanism within the proposed composite electrolytes.

Anatase TiO2 as a Cheap and Sustainable Buffering Filler for Silicon Nanoparticles in Lithium-Ion Battery Anodes.

The design of effective supporting matrices to efficiently cycle Si nanoparticles is often difficult to achieve and requires complex preparation strategies. In this work, we present a simple synthesis of low-cost and environmentally benign aAnatase TiO2 nanoparticles as buffering filler for Si nanoparticles (Si@TiO2 ). The average anatase TiO2 crystallite size was approximately 5 nm. A complete structural, morphological, and electrochemical characterization was performed. Electrochemical test results show very good specific capacity values of up to 1000 mAh g-1 and cycling at several specific currents, ranging from 500 to 2000 mA g-1 , demonstrating a very good tolerance to high cycling rates. Postmortem morphological analysis shows very good electrode integrity after 100 cycles at 500 mA g-1 specific current.

Immobilization and delivery of biologically active Lipoxin A4 using electrospinning technology.

Lipoxin (LX)A4 is a lipoxygenase-formed arachidonic acid metabolite with potent anti-inflammatory, pro-resolution properties. Its therapeutic efficacy has been largely demonstrated in a variety of cellular, preclinical and clinical models. Among these, periodontal disease, where LXA4 promotes tissue repair, also by modulating functions of human periodontal ligament stem cells (hPDLSCs). As medicated biomembranes may be particularly useful in clinical settings, where local stimulation of tissue repair is needed, we used electrospinning to embed LXA4 in membranes made of poly(ethylene oxide) (PEO) and poly(d,l-lactide) (PDLLA). These membranes were fully characterized by scanning electron microscopy, differential scanning calorimetry and biocompatibility with hPDLSCs. Here, we report that LXA4 is retained in these membranes and that ∼15-20% of the total LXA4 amount added to the reaction can be eluted from the membranes using an aqueous buffered medium. The eluted LXA4 fully retained its capability to stimulate hPDLSC proliferation. A similar effect was obtained by adding directly the LXA4-containing membranes to cells. These results demonstrate for the first time that LXA4 can be incorporated into biomembranes, which may be useful to combat local inflammation and promote tissue repair in selected clinical settings.

New Approach in Translational Medicine: Effects of Electrolyzed Reduced Water (ERW) on NF-κB/iNOS Pathway in U937 Cell Line under Altered Redox State.

It is known that increased levels of reactive oxygen species (ROS) and reactive nitrogen species (RNS) can exert harmful effects, altering the cellular redox state. Electrolyzed Reduced Water (ERW) produced near the cathode during water electrolysis exhibits high pH, high concentration of dissolved hydrogen and an extremely negative redox potential. Several findings indicate that ERW had the ability of a scavenger free radical, which results from hydrogen molecules with a high reducing ability and may participate in the redox regulation of cellular function. We investigated the effect of ERW on H2O2-induced U937 damage by evaluating the modulation of redox cellular state. Western blotting and spectrophotometrical analysis showed that ERW inhibited oxidative stress by restoring the antioxidant capacity of superoxide dismutase, catalase and glutathione peroxidase. Consequently, ERW restores the ability of the glutathione reductase to supply the cell of an important endogenous antioxidant, such as GSH, reversing the inhibitory effect of H2O2 on redox balance of U937 cells. Therefore, this means a reduction of cytotoxicity induced by peroxynitrite via a downregulation of the NF-κB/iNOS pathway and could be used as an antioxidant for preventive and therapeutic application. In conclusion, ERW can protect the cellular redox balance, reducing the risk of several diseases with altered cellular homeostasis such as inflammation.

Analytical methods for the endocrine disruptor compounds determination in environmental water samples.

The potential risk of exposure to different xenobiotics, which can modulate the endocrine system and represent a treat for the wellness of an increasing number of people, has recently drawn the attention of international environmental and health agencies. Several agents, characterized by structural diversity, may interfer with the normal endocrine functions that regulate cell growth, homeostasis and development. Substances such as pesticides, herbicides, plasticizers, metals, etc. having endocrine activity (EDCs) are used in agriculture and industry and are also used as drugs for humans and animals. A difficulty in the analytical determination of these substances is the complexity of the matrix in which they are present. In fact, the samples most frequently analyzed consist of groundwater and surface water, including influent and effluent of wastewater treatment plants and drinking water. In this review, several sample pretreatment protocols, assays and different instrumental techniques recently used in the EDCs determination have been considered. This review concludes with a paragraph in which the most recent hyphenated-instrument techniques are treated, highlighting their sensitivity and selectivity for the analyses of environmental water samples.

Single-Walled Carbon Nanotubes in Highly Viscous Media: A Comparison between the Dispersive Agents [BMIM][BF4 ], L121, and Triton X-100.

Dispersions of single-walled carbon nanotubes (SWNTs) have been prepared by using the room-temperature ionic liquid [BMIM][BF4 ] (1-butyl-3-methylimidazolium tetrafluoroborate), the triblock copolymer Pluronic L121 [poly(ethylene oxide)5 -poly(propylene oxide)68 -poly(ethylene oxide)5 ] and the non-ionic surfactant Triton X-100 (TX100) in the pure state. The size of the SWNTs aggregates and the dispersion degree in the three viscous systems depend on the sonication time, as highlighted by UV/Vis/NIR spectroscopy and optical microscopy analysis. A nonlinear increase in conductivity can be observed as a function of the SWNTs loading, as suggested by electrochemical impedance spectroscopy. The generation of a three-dimensional network of SWNTs showing a viscoelastic gel-like behavior above a critical percolation concentration has been found at 25 °C in all the investigated systems by oscillatory rheology measurements.

Phase behaviour, transport properties, and interactions in Li-salt doped ionic liquids.

We report on the influence of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) doping on the glass transition temperature (Tg), the ionic conductivity, and Li-ion coordination of two dicationic ionic liquids (DILs) based on the TFSI anion. The results are compared to the behaviour of traditional mono-cationic ionic liquids. The cations of the DILs contain two imidazolium rings, connected by a decane hydrocarbon chain. Homogeneous mixtures of these ILs and LiTFSI can be obtained in a large concentration range. With increasing Li-salt concentration the ionic conductivity decreases whereas the glass transition temperature increases in both systems. However, the influence of the salt doping on the ionic conductivity and the glass transition temperature is low compared to typical mono-cationic ionic liquids, based on for example the pyrrolidinium cation and the TFSI anion. This behaviour is mirrored in the average coordination number of TFSI anions around Li-ions, determined by Raman spectroscopy. The coordination number is systematically lower in the DILs, suggesting a connection between the difference in the Li-ion environment and the behaviour of the glass transition and the ionic conductivity. A Tg-scaled Arrhenius plot of the ionic conductivity shows that the ionic conductivity for all LiTFSI concentrations has the same temperature dependence, i.e., the fragility of the liquid is the same. This implies that the conduction process is dominated by the viscous properties of the liquids over the entire concentration range. This provides further support for linking the local environment of the Li-ions to the glass transition and conduction process in the ionic liquid/salt mixtures.

Thermal properties and ionic conductivity of imidazolium bis(trifluoromethanesulfonyl)imide dicationic ionic liquids.

We report on the thermal and transport properties of new dicationic ionic liquids. The new ionic liquids are based on the bis(trifluoromethanesulfonyl)imide [NTf(2)](-) anion and a cation that contains two imidazolium rings, connected by either a pentane or a decane hydrocarbon chain and different side groups. We have investigated the conductivity and the thermal properties by dielectric spectroscopy and differential scanning calorimetry, respectively. Our results show that the length of the alkyl chain on the cation has no, or weak, influence on the glass transition temperature, T(g), whereas the presence of rigid aromatic side groups has a strong influence increase T(g). The highest ionic conductivity is 5.9 x 10(-4) S cm(-1) at 298 K for an ionic liquid with a decane chain and one methyl group on each imidazolium ring. The conductivity results correlate well with the glass transition temperatures. This shows that the flexibility of the geminal cations is very important for the conductivity. However, the presence of nonflexible aromatic side groups on the imidazolium ring decreases the flexibility and hence the mobility.

Correlation of AC-impedance and in situ X-ray spectra of LiCoO2.

In-situ X-ray and AC-impedance spectra have been obtained simultaneously during the deintercalation of lithium from LiCoO2 using a specially designed electrochemical cell. The AC-dispersions have been correlated with the cell parameters obtained from the X-ray spectra. The correlation confirms previous hypothesis on the interpretation of the AC-dispersions in terms of an equivalent circuit comprising an element that relates the change of the intrinsic electronic conductivity, occurring at the early stages of deintercalation, to the semiconductor to metal transition caused by the change of the cell parameters.

Conductivities and transport properties of gelled electrolytes with and without an ionic liquid for Li and Li-ion batteries.

Conductivity and transport properties have been determined for gelled polymer electrolytes of three compositions: a base PVdF-polymer gel with organic carbonate solvents as plasticizers and LiN(SO(2)C(2)F(5))(2) electrolyte, a second polymer electrolyte with 5 mass % 1-ethyl-3-methylimidazolium bisperfluoroethylsulfonyl imide (EMI-BETI) added to the base polymer electrolyte, and a third PVdF polymer electrolyte using only EMI-BETI as the plasticizer. Conductivities were studied over the temperature range +25 to -40 degrees C, and for all three gels, the temperature dependence of the conductivities was found to follow the VTF equation, which is consistent with the free volume model for ion transport. For the gel containing 5 mass % EMI-BETI, transport numbers were determined from +50 to -20 degrees C and were found to decrease as the temperature decreased. Although there are no theoretical models to treat and interpret the temperature dependence of transport numbers, we found that a modified VTF equation resulted in an excellent fit to the temperature dependence of the transport number, which is another confirmation of a free volume model for transport in these gelled polymer electrolytes.

Nanocomposite lithium ion conducting membranes.

This review describes the properties and characteristics of a class of membranes formed by blends of a lithium salt, LiX, where X is preferably a large soft anion, such as ClO(4) or N(CF(3)SO(2))(2), and a high molecular weight polymer containing Li(+)-coordinating group, such as polyethylene oxide (PEO) with the dispersion of selected ceramic powders, such as TiO(2), Al(2)O(3), and SiO(2), at the nanoscale particle size. These nanocomposite membranes behave as lithium polymer electrolytes, that is, they exhibit a high lithium ion conductivity. Because of this property, the PEO-LiX nanocomposite electrolytes may find an important application as separators in advanced, rechargeable lithium polymer batteries.