Cycling performance of lithium metal polymer cells assembled with ionic liquid and poly(3-methyl thiophene)/carbon nanotube composite cathode

A poly(3-methylthiophene) (PMT)/multi-walled carbon nanotube (CNT) composite is synthesized by in situ chemical polymerization. The PMT/CNT composite is used as an active cathode material in lithium metal polymer cells assembled with ionic liquid (IL) electrolytes. The IL electrolyte consists of 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF4) and LiBF4. A small amount of vinylene carbonate is added to the IL electrolyte to prevent the reductive decomposition of the imidazolium cation in EMIBF4. A porous poly(vinylidene fluoride-co-hexafluoropropylene) (P(VdF-co-HFP)) film is used as a polymer membrane for assembling the cells. Electrochemical properties of the PMT/CNT composite electrode in the IL electrolyte are evaluated and the effect of vinylene carbonate on the cycling performance of the lithium metal polymer cells is investigated. The cells assembled with a non-flammable IL electrolyte and a PMT/CNT composite cathode are promising candidates for high-voltage–power sources with enhanced safety.

Substrate-induced coagulation (SIC) of nano-disperse carbon black in non-aqueous media : a method of manufacturing highly conductive cathode materials for Li-ion batteries by self-assembly

Substrate-induced coagulation (SIC) is a coating process based on self-assembly for coating different surfaces with fine particulate materials. The particles are dispersed in a suitable solvent and the stability of the dispersion is adjusted by additives. When a surface, pre-treated with a flocculant e.g. a polyelectrolyte, is dipped into the dispersion, it induces coagulation resulting in the deposition of the particles on the surface. A non-aqueous SIC process for carbon coating is presented, which can be performed in polar, aprotic solvents such as N-Methyl-2- pyrrolidinone (NMP). Polyvinylalcohol (PVA) is used to condition the surface of substrates such as mica, copperfoil, silicon-wafers and lithiumcobalt oxide powder, a cathode material used for Li-ion batteries. The subsequent SIC carbon coating produces uniform layers on the substrates and causes the conductivity of lithiumcobalt oxide to increase drastically, while retaining a high percentage of active battery material.

Characterization and evaluation of BaCo0.7Fe0.2Nb0.1O3−δ as a cathode for proton-conducting solid oxide fuel cells

This study characterizes BaCo0.7Fe0.2Nb0.1O3−δ (BCFN) perovskite oxide and evaluates it as a potential cathode material for proton-conducting SOFCs with a BaZr0.1Ce0.7Y0.2O3-δ (BZCY) electrolyte. A four-probe DC conductivity measurement demonstrated that BCFN has a modest electrical conductivity of 2–15 S cm−1 in air with p-type semiconducting behavior. An electrical conductivity relaxation test showed that BCFN has higher Dchem and Kchem than the well-known Ba0.5Sr0.5Co0.8Fe0.2O3−δ oxide. In addition, it has relatively low thermal expansion coefficients (TECs) with values of 18.2 × 10−6 K−1 and 14.4 × 10−6 K−1 at temperature ranges of 30–900 °C and 30–500 °C, respectively. The phase reaction between BCFN and BZCY was investigated using powder and pellet reactions. EDX and XRD characterizations demonstrated that BCFN had lower reactivity with the BZCY electrolyte than strontium-containing perovskite oxides such as SrCo0.9Nb0.1O3-δ and Ba0.6Sr0.4Co0.9Nb0.1O3−δ. The impedance of BCFN was oxygen partial pressure dependent. Introducing water into the cathode atmosphere reduced the size of both the high-frequency and low-frequency arcs of the impedance spectra due to facilitated proton hopping. The cathode polarization resistance and overpotential at a current density of 100 mA cm−2 were 0.85 Ω cm−2 and 110 mV in dry air, which decreased to 0.43 Ω cm−2 and 52 mV, respectively, in wet air (∼3% H2O) at 650 °C. A decrease in impedance was also observed with polarization time; this was possibly caused by polarization-induced microstructure optimization. A promising peak power density of ∼585 mW cm−2 was demonstrated by an anode-supported cell with a BCFN cathode at 700 °C.

Deactivation and regeneration of oxygen reduction reactivity on double perovskite Ba2Bi0.1Sc0.2Co1.7O6−x cathode for intermediate-temperature solid oxide fuel cells

in situ high-temperature X-ray diffraction and thermal gravimetric- differential thermal analysis on room-temperature powder, as well as X-ray diffraction, Raman spectroscopy, and transmission electron microscopy on quenched powder, were applied to study crystal structure and phase transformations in Ba₂Bi_0.1Sc_0.2Co _1.7O_6-x (BBSC). Heating BBSC in air to over 800 °C produces a pure cubic phase with space group Fm3m (no. 225), and cooling down below 800 °C leads to a mixture of three noncubic phases including an unknown phase between 200 and 650 °C, a 2H hexagonal BaCoO3 with space group P63/mmc (no. 194) between 600 and 800 °C, and an intermediate phase at 800 °C. These three phases exist concurrently with the major cubic phase. The weight gain and loss between 300 and 900 °C suggest the occurrence of cobalt reduction, oxidation, and disproportion reactions with dominant reduction reaction at above 600 °C. The thermal expansion of BBSC was also examined by dilatometry. BBSC has a highly temperature-dependent thermal expansion coefficient which relates well with its structure evolution. Furthermore, the oxygen reduction reaction (ORR) of BBSC was probed by symmetrical cell and three-electrode configurations. The presence of hexagonal phase at 700 °C rarely affects the ORR performance of BBSC as evidenced by a slight increase of its area-specific resistance (ASR) value following 48 h of testing in this three-electrode configuration. This observation is in contrast to the commonly held point of view that noncubic phase deteriorates performance of perovskite compounds (especially in oxygen transport applications). Moreover, cathodic polarization treatment, for example, current discharge from BBSC (tested in three-electrode configuration), can be utilized to recover the original ORR performance. The cubic structure seems to be retained on the cathodic polarization - the normal cathode operating mode in fuel cells. Stable 72-h performance of BBSC in cathodic polarization mode further confirms that despite the presence of phase impurities, BBSC still demonstrates good performance between 500 and 700 °C, the desired intermediate operating temperature in solid oxide fuel cells.

The significant effect of the phase composition on the oxygen reduction reaction activity of a layered oxide cathode

Layered oxides of Sr4Fe4Co2O13 (SFC2) which contains alternating perovskite oxide octahedral and polyhedral oxide double layers are attractive for their mixed ionic and electronic conducting and oxygen reduction reaction properties. In this work, we used the EDTA–citrate synthesis technique to prepare SFC2 and vary the calcination temperature between 900 and 1100 _C to obtain SFC2, containing different phase content of perovskite (denoted as SFC-P) and (Fe,Co) layered oxide phases (SFC-L). Rietveld refinements show that the SFC-P phase content increased from _39 wt% to _50 wt% and _61 wt% as the calcination temperature increased from 900 _C (SFC2-900) to 1000 _C (SFC2-1000) and 1050 _C (SFC2-1050). At 1100 _C (SFC2-1100), SFC-P became the dominant phase. The oxygen transport properties (e.g. oxygen chemical diffusion coefficient and oxygen permeability), electrical conductivity and oxygen reduction reaction activity is enhanced in the order of SFC2-1000, SFC2-1100 and SFC2-1050. The trend established here therefore negates the hypothesis that the perovskite phase content correlates with the oxygen transport property enhancement. The results suggest instead that there is an optimum composition value (e.g. 61 wt% of SFC-L for SFC2-1050 in this work) on which synergistic effects take place between the SFC-P and SFC-L phase.

Effect of magnetic treatment on microstructure and cycle performance of LiFePO4/C cathode material

LiFePO4/C composite was prepared by hydrothermal synthesis along with a magnetic treatment method. The LiFePO4/C composite synthesized without magnetic treatment is an integrated rhombic shape crystal, whereas the LiFePO4/C material synthesized with magnetic treatment presents a rhombus shape which is self-assembled by a number of small crystal particles with an average size of about 100 nms. The capacity retention for the LiFePO4/C cathode material synthesized without magnetic treatment is only 77% after 30 charge-discharge cycles at 0.2 C, but the LiFePO4/C composite synthesized with magnetic treatment has a capacity retention of 100% after 100 charge-discharge cycles at 1 C and 5 C. It suggests that magnetic treatment can remove Fe3+ cations effectively during the preparation process and enhance the cycle performance of the LiFePO4/C material.

Sulfur-doped porous reduced graphene oxide hollow nanosphere frameworks as metal-free electrocatalysts for oxygen reduction reaction and as supercapacitor electrode materials.

Chemical doping with foreign atoms is an effective approach to significantly enhance the electrochemical performance of the carbon materials. Herein, sulfur-doped three-dimensional (3D) porous reduced graphene oxide (RGO) hollow nanosphere frameworks (S-PGHS) are fabricated by directly annealing graphene oxide (GO)-encapsulated amino-modified SiO2 nanoparticles with dibenzyl disulfide (DBDS), followed by hydrofluoric acid etching. The XPS and Raman spectra confirmed that sulfur atoms were successfully introduced into the PGHS framework via covalent bonds. The as-prepared S-PGHS has been demonstrated to be an efficient metal-free electrocatalyst for oxygen reduction reaction (ORR) with the activity comparable to that of commercial Pt/C (40%) and much better methanol tolerance and durability, and to be a supercapacitor electrode material with a high specific capacitance of 343 F g(-1), good rate capability and excellent cycling stability in aqueous electrolytes. The impressive performance for ORR and supercapacitors is believed to be due to the synergistic effect caused by sulfur-doping enhancing the electrochemical activity and 3D porous hollow nanosphere framework structures facilitating ion diffusion and electronic transfer.

Three-dimensional numerical simulation of blood flow in mouse aortic arch around atherosclerotic plaques

Atherosclerosis is a progressive disease, involving the build-up of lipid streaks in artery walls, leading to plaques. Understanding the development of atherosclerosis and plaque vulnerability is critically important since plaque rupture can result in heart attack or stroke. Plaques can be divided into two distinct types: those likely to rupture (vulnerable) or less likely to rupture (stable). In the last decade, researchers have been interested in studying the influence of the mechanical effects (blood shear stress, pressure forces and structural stress) on the plaque formation, progression and rupture processes but no general agreement has been found. The purpose of the present work is to include more realistic conditions for the numerical calculations of the blood flow by implementing real geometries with plaques in the numerical model. Hemodynamical parameters are studied in both diseased and healthy configurations. The healthy configuration is obtained by removing numerically the plaques from three dimensional geometries obtained by micro-computed tomography. A new hemodynamical parameter is also introduced to relate the location of plaques to the characteristics of the flow in the healthy configuration. © 2014 .