Project description:Zeolite N is a synthetic zeolite of the EDI framework family from the more than 200 known zeolite types. Previous experimental laboratory and field data show that zeolite N has a high capacity for exchange of ions. Computational modelling and simulation techniques are effective tools that help explain the atomic-scale behaviour of zeolites under different processing conditions and allow comparison with experiment. In this study, the ion exchange behaviour of synthetic zeolite N in an aqueous environment is investigated by molecular dynamics simulations. The exchange mechanism of K+ extra-framework cations with alkaline and alkaline-earth cations NH4+, Li+, Na+, Rb+, Cs+, Mg2+ and Ca2+ is explored in different crystallographic directions inside the zeolite N structure. Moreover, the effect of different framework partial charges on MD simulation results obtained from different DFT calculations are examined. The results show that the diffusion and exchange of cations in zeolite N are affected by shape and size of channels controlling the ion exchange flow as well as the nature of cation, ionic size and charge density.
Project description:In spite of the abundant literature, questions on the biological action of Li+ are far from being answered. In the present paper we demonstrate that modification of the salt composition of the medium for actin polymerization, by gradually replacing K+ with Li+, leads to a dose-related change in the time course of actin assembly. The presence of Li+ influences actin polymerization in vitro by enhancing nucleation and decreasing critical monomer concentration at steady state. Furthermore, Li+ stabilizes actin polymers mainly by lowering the absolute value of the dissociation rate constant (K-) and shifting (towards lower values of actin monomer concentrations) the range of G-actin concentrations in which filament-subunit flux can occur. The influence of Li+ on actin and tubulin polymerization in vitro suggests that cytoskeletal structures could be some of the cytoplasmic targets of this ion.
Project description:Solid-state lithium-based batteries offer higher energy density than their Li-ion counterparts. Yet they are limited in terms of negative electrode discharge performance and require high stack pressure during operation. To circumvent these issues, we propose the use of lithium-rich magnesium alloys as suitable negative electrodes in combination with Li6PS5Cl solid-state electrolyte. We synthesise and characterise lithium-rich magnesium alloys, quantifying the changes in mechanical properties, transport, and surface chemistry that impact electrochemical performance. Increases in hardness, stiffness, adhesion, and resistance to creep are quantified by nanoindentation as a function of magnesium content. A decrease in diffusivity is quantified with 6Li pulsed field gradient nuclear magnetic resonance, and only a small increase in interfacial impedance due to the presence of magnesium is identified by electrochemical impedance spectroscopy which is correlated with x-ray photoelectron spectroscopy. The addition of magnesium aids contact retention on discharge, but this must be balanced against a decrease in lithium diffusivity. We demonstrate via electrochemical testing of symmetric cells at 2.5 MPa and 30∘C that 1% magnesium content in the alloy increases the stripping capacity compared to both pure lithium and higher magnesium content alloys by balancing these effects.
Project description:To increase the energy storage density of lithium-ion batteries, silicon anodes have been explored due to their high capacity. One of the main challenges for silicon anodes are large volume variations during the lithiation processes. Recently, several high-performance schemes have been demonstrated with increased life cycles utilizing nanomaterials such as nanoparticles, nanowires, and thin films. However, a method that allows the large-scale production of silicon anodes remains to be demonstrated. Herein, we address this question by suggesting new scalable nanomaterial-based anodes. Si nanoparticles were grown on nanographite flakes by aerogel fabrication route from Si powder and nanographite mixture using polyvinyl alcohol (PVA). This silicon-nanographite aerogel electrode has stable specific capacity even at high current rates and exhibit good cyclic stability. The specific capacity is 455 mAh g-1 for 200th cycles with a coulombic efficiency of 97% at a current density 100 mA g-1.
Project description:Ryanodine receptor channels at calcium release sites of cardiac myocytes operate on the principle of calcium-induced calcium release. In vitro experiments revealed competition of Ca2+ and Mg2+ in the activation of ryanodine receptors (RyRs) as well as inhibition of RyRs by Mg2+. The impact of RyR modulation by Mg2+ on calcium release is not well understood due to the technical limitations of in situ experiments. We turned instead to an in silico model of a calcium release site (CRS), based on a homotetrameric model of RyR gating with kinetic parameters determined from in vitro measurements. We inspected changes in the activity of the CRS model in response to a random opening of one of 20 realistically distributed RyRs, arising from Ca2+/Mg2+ interactions at RyR channels. Calcium release events (CREs) were simulated at a range of Mg2+-binding parameters at near-physiological Mg2+ and ATP concentrations. Facilitation of Mg2+ binding to the RyR activation site inhibited the formation of sparks and slowed down their activation. Impeding Mg-binding to the RyR activation site enhanced spark formation and speeded up their activation. Varying Mg2+ binding to the RyR inhibition site also dramatically affected calcium release events. Facilitation of Mg2+ binding to the RyR inhibition site reduced the amplitude, relative occurrence, and the time-to-end of sparks, and vice versa. The characteristics of CREs correlated dose-dependently with the effective coupling strength between RyRs, defined as a function of RyR vicinity, single-channel calcium current, and Mg-binding parameters of the RyR channels. These findings postulate the role of Mg2+ in calcium release as a negative modulator of the coupling strength among RyRs in a CRS, translating to damping of the positive feedback of the calcium-induced calcium-release mechanism.
Project description:We have used rapid pressure jump and stopped-flow fluorometry to investigate calcium and magnesium binding to F29W chicken skeletal troponin C. Increased pressure perturbed calcium binding to the N-terminal sites in the presence and absence of magnesium and provided an estimate for the volume change upon calcium binding (-12 mL/mol). We observed a biphasic response to a pressure change which was characterized by fast and slow reciprocal relaxation times of the order 1000/s and 100/s. Between pCa 8-5.4 and at troponin C concentrations of 8-28 muM, the slow relaxation times were invariant, indicating that a protein isomerization was rate-limiting. The fast event was only detected over a very narrow pCa range (5.6-5.4). We have devised a model based on a Monod-Wyman-Changeux cooperative mechanism with volume changes of -9 and +6 mL/mol for the calcium binding to the regulatory sites and closed to open protein isomerization steps, respectively. In the absence of magnesium, we discovered that calcium binding to the C-terminal sites could be detected, despite their position distal to the calcium-sensitive tryptophan, with a volume change of +25 mL/mol. We used this novel observation to measure competitive magnesium binding to the C-terminal sites and deduced an affinity in the range 200-300 muM (and a volume change of +35 mL/mol). This affinity is an order of magnitude tighter than equilibrium fluorescence data suggest based on a model of direct competitive binding. Magnesium thus indirectly modulates binding to the N-terminal sites, which may act as a fine-tuning mechanism in vivo.
Project description:We demonstrate a cross-linked, 3D conductive network structure, porous silicon@carbon nanofiber (P-Si@CNF) anode by magnesium thermal reduction (MR) and the electrospinning methods. The P-Si thermally reduced from silica (SiO2) preserved the monodisperse spheric morphology which can effectively achieve good dispersion in the carbon matrix. The mesoporous structure of P-Si and internal nanopores can effectively relieve the volume expansion to ensure the structure integrity, and its high specific surface area enhances the multi-position electrical contact with the carbon material to improve the conductivity. Additionally, the electrospun CNFs exhibited 3D conductive frameworks that provide pathways for rapid electron/ion diffusion. Through the structural design, key basic scientific problems such as electron/ion transport and the process of lithiation/delithiation can be solved to enhance the cyclic stability. As expected, the P-Si@CNFs showed a high capacity of 907.3 mAh g-1 after 100 cycles at a current density of 100 mA g-1 and excellent cycling performance, with 625.6 mAh g-1 maintained even after 300 cycles. This work develops an alternative approach to solve the key problem of Si nanoparticles' uneven dispersion in a carbon matrix.
Project description:The modification of silicon nanoparticles for lithium-ion battery anode materials has been a hot exploration subject in light of their excellent volume buffering performance. However, huge volume expansion leads to an unstable solid electrolyte interface (SEI) layer on the surface of the silicon anode material, resulting in short cell cycle life, which is an important factor limiting the application of silicon nanoparticles. Herein, a dual protection strategy to improve the cycling stability of commercial silicon nanoparticles is demonstrated. Specifically, the Si/s-C@TiO2 composite was produced by the hydrothermal method to achieve the embedding of commercial silicon nanoparticles in spherical carbon and the coating of the amorphous TiO2 shell on the outer surface. Buffering of silicon nanoparticle volume expansion by spherical carbon and also the stabilization of the TiO2 shell with high mechanical strength on the surface constructed a stable outer surface SEI layer of the new Si/s-C@TiO2 electrode during longer cycling. In addition, the spherical carbon and lithiated TiO2 further enhanced the electronic and ionic conductivity of the composite. Electrochemical measurements showed that the Si/s-C@TiO2 composite exhibited excellent lithium storage performance (780 mA h g-1 after 100 cycles at a current density of 0.2 A g-1 with a coulombic efficiency of 99%). Our strategy offers new ideas for the production of high stability and high-performance anode materials for lithium-ion batteries.
Project description:Silicon is an attractive anode material for lithium-ion batteries. However, silicon anodes have the issue of volume change, which causes pulverization and subsequently rapid capacity fade. Herein, we report organic binder and conducting diluent-free silicon-carbon 3D electrodes as anodes for lithium-ion batteries, where we replace the conventional copper (Cu) foil current collector with highly conductive carbon fibers (CFs) of 5-10 μm in diameter. We demonstrate here the petroleum pitch (P-pitch) which adequately coat between the CFs and Si-nanoparticles (NPs) between 700 and 1000 °C under argon atmosphere and forms uniform continuous layer of 6-14 nm thick coating along the exterior surfaces of Si-NPs and 3D CFs. The electrodes fabricate at 1000 °C deliver capacities in excess of 2000 mA h g-1 at C/10 and about 1000 mA h g-1 at 5 C rate for 250 cycles in half-cell configuration. Synergistic effect of carbon coating and 3D CF electrode architecture at 1000 °C improve the efficiency of the Si-C composite during long cycling. Full cells using Si-carbon composite electrode and Li1.2Ni0.15Mn0.55Co0.1O2-based cathode show high open-circuit voltage of >4 V and energy density of >500 W h kg-1. Replacement of organic binder and copper current collector by high-temperature binder P-pitch and CFs further enhances energy density per unit area of the electrode. It is believed that the study will open a new realm of possibility for the development of Li-ion cell having almost double the energy density of currently available Li-ion batteries that is suitable for electric vehicles.
Project description:Silicon has emerged as the most promising high-capacity material for lithium-ion batteries. Waste glass can be a potential low cost and environmentally benign silica resource enabling production of nanosized silicon at the industry level. Windshields are generally made of laminated glass comprising two separate glass bonded together with a layer of polyvinyl butyral sandwiched between them. Herein, silicon/carbon nanocomposites are fabricated from windshields for the first time via magnesiothermic reduction and facile carbonization process using both waste glass and polyvinyl butyral as silica and carbon sources, respectively. High purity reduced silicon has unique 3-dimensional nanostructure with large surface area. Furthermore, the incorporation of carbon in silicon enable to retain the composite anodes highly conductive and mechanically robust, thus providing enhanced cycle stability.