Influence of vanillic acid immobilization in Nafion membranes on intramembrane diffusion and structural properties.

Pulsed field gradient (PFG) NMR in combination with quasielastic neutron scattering (QENS) was used to investigate self-diffusion of water and acetone in Nafion membranes with and without immobilized vanillic acid (VA). Complementary characterization of these membranes was performed by small angle X-ray scattering (SAXS) and NMR relaxometry. This study was motivated by the recent data showing that an organic acid, such as VA, in Nafion can preserve its catalytic activity in the presence of water even at high intra-polymer water concentrations corresponding up to 100% ambient relative humidity. However, there is currently no clear understanding of how immobilized organic acid molecules influence the microscopic transport properties and related structural properties of Nafion. Microscopic diffusion data measured by PFG NMR and QENS are compared for Nafion with and without VA. For displacements smaller than the micrometer-sized domains previously reported for Nafion, the VA addition was not observed to lead to any significant changes in the water and/or acetone self-diffusivity measured by each technique inside Nafion. However, the reported PFG NMR data present evidence of a different influence of acetone concentration in the membranes with and without VA on the water permeance of the interfaces between neighboring micrometer-sized domains. The reported diffusion data are correlated with the results of SAXS structural characterization and NMR relaxation data for water and acetone.

Transition between Different Diffusion Regimes and Its Relationship with Structural Properties in Nafion by High Field Diffusion NMR in Combination with Small-Angle X-ray and Neutron Scattering.

Pulsed field gradient (PFG) NMR at high field was utilized to directly observe a transition between two different diffusion regimes in a Nafion 117 membrane loaded with water and acetone. Although water self-diffusivity at small water loadings was observed to be diffusion time-independent in the limit of small and large diffusion times, it showed a significant decrease with increasing diffusion time at intermediate times corresponding to root mean square displacements on the order of several microns. Under our experimental conditions, no self-diffusivity dependence on diffusion time was found for water at large water loadings and for acetone at all studied acetone loadings. The diffusion time-dependent self-diffusivity at small water concentration is explained by the existence of finite domains of interconnected water channels with sizes in the range of several microns that form in Nafion in the presence of acetone. The domain sizes and permeance of transport barriers separating adjacent domains are estimated based on the measured PFG NMR data. At large water concentrations, the water channels form a fully interconnected network, resulting in time-independent self-diffusivity. The absence of such a percolation-like transition with increasing molecular concentration for acetone is attributed to a difference in the regions available for water and acetone diffusion in Nafion. The diffusion data are correlated with and supported by structural data obtained using small-angle X-ray and neutron scattering techniques. These techniques reveal distinct water channels with radial dimensions in the nanometer range increasing upon water addition, while acetone appears to be in an interfacial perfluoroether region, reducing the size of the radial channel dimension.

Porous graphitic carbon loading ultra high sulfur as high-performance cathode of rechargeable lithium-sulfur batteries.

Porous graphitic carbon of high specific surface area of 1416 m(2) g(-1) and high pore volume of 1.11 cm(3) g(-1) is prepared by using commercial CaCO3 nanoparticles as template and sucrose as carbon source followed by 1200 °C high-temperature calcination. Sulfur/porous graphitic carbon composites with ultra high sulfur loading of 88.9 wt % (88.9%S/PC) and lower sulfur loading of 60.8 wt % (60.8%S/PC) are both synthesized by a simple melt-diffusion strategy, and served as cathode of rechargeable lithium-sulfur batteries. In comparison with the 60.8%S/PC, the 88.9%S/PC exhibits higher overall discharge capacity of 649.4 mAh g(-1)(S-C), higher capacity retention of 84.6% and better coulombic efficiency of 97.4% after 50 cycles at a rate of 0.1C, which benefits from its remarkable specific capacity with such a high sulfur loading. Moreover, by using BP2000 to replace the conventional acetylene black conductive agent, the 88.9% S/PC can further improve its overall discharge capacity and high rate property. At a high rate of 4C, it can still deliver an overall discharge capacity of 387.2 mAh g(-1)(S-C). The porous structure, high specific surface area, high pore volume and high electronic conductivity that is originated from increased graphitization of the porous graphitic carbon can provide stable electronic and ionic transfer channel for sulfur/porous graphitic carbon composite with ultra high sulfur loading, and are ascribed to the excellent electrochemical performance of the 88.9%S/PC.

Facile synthesis of hierarchical micro/nanostructured MnO material and its excellent lithium storage property and high performance as anode in a MnO/LiNi0.5Mn1.5O(4-δ) lithium ion battery.

Hierarchical micro/nanostructured MnO material is synthesized from a precursor of MnCO3 with olive shape that is obtained through a facile one-pot hydrothermal procedure. The hierarchical micro/nanostructured MnO is served as anode of lithium ion battery together with a cathode of spinel LiNi0.5Mn1.5O(4-δ) material, which is synthesized also from the precursor of MnCO3 with olive shape through a different calcination process. The structures and compositions of the as-prepared materials are characterized by TGA, XRD, BET, SEM, and TEM. Electrochemical tests of the MnO materials demonstrate that it exhibit excellent lithium storage property. The MnO material in a MnO/Li half cell can deliver a reversible capacity of 782.8 mAh g(-1) after 200 cycles at a rate of 0.13 C, and a stable discharge capacity of 350 mAh g(-1) at a high rate of 2.08 C. Based on the outstanding electrochemical property of the MnO material and the LiNi0.5Mn1.5O(4-δ) as well, the MnO/LiNi0.5Mn1.5O(4-δ) full cell has demonstrated a high discharge specific energy ca. 350 Wh kg(-1) after 30 cycles at 0.1 C with an average high working voltage at 3.5 V and a long cycle stability. It can release a discharge specific energy of 227 Wh kg(-1) after 300 cycles at a higher rate of 0.5 C. Even at a much higher rate of 20 C, the MnO/LiNi0.5Mn1.5O(4-δ) full cell can still deliver a discharge specific energy of 145.5 Wh kg(-1). The excellent lithium storage property of the MnO material and its high performance as anode in the MnO/LiNi0.5Mn1.5O(4-δ) lithium ion battery is mainly attributed to its hierarchical micro/nanostructure, which could buffer the volume change and shorten the diffusion length of Li(+) during the charge/discharge processes.