Self-assembled cubic-hexagonal perovskite nanocomposite as intermediate-temperature solid oxide fuel cell cathode

Self-assembly is an emerging strategy for preparing composite cathodes with good oxygen electrochemical reduction activity and congenital chemical compatibility for intermediate-temperature solid oxide fuel cell (IT-SOFC). Here we report that a self-assembled BaCo_0.6Zr_0.4O_3-δ (BZC-BC) nanocomposite is prepared through one-pot glycine-nitrate process and exhibits high cathode performance. The BZC-BC nanocomposite is composed of 62 mol% cubic perovskite BaZr_0.82Co_0.18O_3-δ (BZC) as an ionic conductor and 38 mol% hexagonal perovskite BaCo_0.96Zr_0.04O_2.6+δ (12H-BC) as a mixed ionic and electronic conductor. The BZC-BC nanocomposite has the pomegranate-like particles aggregated with a larger number of nanoparticles (50-100 nm) which greatly enlarge the three-phase boundary sites. The BZC-BC nanocomposite exhibits a thermal expansion coefficient of 12.89 × 10⁻⁶ K⁻¹ well-matched with that of Ce_0.8Gd_0.2O_3-δ (12.84 × 10⁻⁶ K⁻¹) electrolyte. The high electro-catalytic activity of BZC-BC nanocomposite cathode for oxygen reduction is reflected by the low polarization resistances of oxygen ions incorporation at cathode/electrolyte interface (0.02823 Ω cm²), oxygen species diffusion (0.03702 Ω cm²) and oxygen adsorptive dissociation (0.07609 Ω cm²) at 700 °C. The single cell with BZC-BC nanocomposite cathode achieves the maximum power density of 1094 mW cm⁻² at 650 °C and shows good stability under 25 h run.     

Low shear rheological behaviour of two-phase mesophase pitch

The low shear rate rheology of two phase mesophase pitches derived from coal tar pitch has been investigated. Particulate quinoline insolubles (QI) stabilised the mesophase spheres against coalescence. Viscosity measurements over the range 10–10⁶ Pa s were made at appropriate temperature ranges. Increasing shear thinning behaviour was evident with increasing mesophase content. At low mesophase contents the dominant effect on the near Newtonian viscosity was temperature but at higher contents it was the shear rate; temperature dependence declined to near zero. The data indicated that agglomeration could be occurring at intermediate mesophase volume fractions, 0.2–0.3. The Krieger–Dougherty function and its emulsion analogue indicated that in this region the mesophase pitch emulsions actually behaved like ‘hard’ sphere systems and the effective volume fraction was estimated as a function of shear rate illustrating the change in extent of agglomeration. At the higher volume fractions approaching the maximum packing fraction, which could only be measured at higher temperatures, the shear thinning behaviour changed in character and it is considered that this is possibly due to shear induced deformation and breakup of dispersed drops in the shear field.     

Output-relevant Variational autoencoder for Just-in-time soft sensor modeling with missing data

Main challenges for developing data-based models lie in the existence of high-dimensional and possibly missing observations that exist in stored data from industry process. Variational autoencoder (VAE) as one of the deep learning methods has been applied for extracting useful information or features from high-dimensional dataset. Considering that existing VAE is unsupervised, an output-relevant VAE is proposed for extracting output-relevant features in this work. By using correlation between process variables, different weight is correspondingly assigned to each input variable. With symmetric Kullback–Leibler (SKL) divergence, the similarity is evaluated between the stored samples and a query sample. According to the values of the SKL divergence, data relevant for modeling are selected. Subsequently, Gaussian process regression (GPR) is utilized to establish a model between the input and the corresponding output at the query sample. In addition, owing to the common existence of missing data in output data set, the parameters and missing data in the GPR are estimated simultaneously. A practical debutanizer industrial process is utilized to illustrate the effectiveness of the proposed method.     

Electrochemical generation of hydrogenated graphene flakes

A cathodic electrochemical method for the exfoliation of graphite to produce hydrogenated graphenic flakes is introduced. The resulting solutions consist of micrometer-sized and predominantly 1–4 layers thick hydrogenated graphenic flakes. In contrast to oxygenation, chemisorption of hydrogen avoids the formation of structural vacancy defects in the exfoliated flakes. Thermal desorption of hydrogen therefore results in graphenic flakes with a low defect density and consequently good electrical conductivity. Cathodic electrochemical exfoliation offers a remarkably simple and effective technique for the production of high quality graphene flakes and their hydrogenated relatives.     

Simultaneous enhancement of the efficiency and stability of organic solar cells using PEDOT:PSS grafted with a PEGME buffer layer

We report a simple processing method to simultaneously improve the efficiency and stability of organic solar cells (OSCs). Poly(4-styrene sulfonate)-doped poly(3,4-ethylenedioxy-thiophene (PEDOT:PSS), widely used as hole transport layer (HTL) in OSCs, tends to accelerate the degradation of devices because of its hygroscopic and acidic properties. In this regard, we have modified PEDOT:PSS to reduce its hygroscopic and acidic properties through a condensation reaction between PEDOT:PSS and poly(ethylene glycol) methyl ether (PEGME) in order to improve the efficiency and stability of OSCs. As a result, the power conversion efficiency (PCE) increased by 21%, from 2.57% up to 3.11%. A better energy level alignment by the reduced work function of the modified PEDOT:PSS with a highest occupied molecular orbital (HOMO) level of poly(3-hexylthiophene-2,5-diyl) (P3HT) is considered the origin of the improved the efficiency. The half-life of OSCs with PEDOT:PSS modified with PEGME buffer layer also increased up to 3.5 times compared to that of devices with pristine PEDOT:PSS buffer layer.     

Monomer casting nylon-6-b-polyether amine copolymers: Synthesis and properties

MC nylon-6-b-polyether amine copolymers were prepared with macro-initiator based on amino-terminated polyether amine functionalized with isocyanate via in-situ polymerization. It was found that the introduction of polyether amine delayed the polymerization process of caprolactam by increasing apparent activation energy and pre-exponential factor, resulting in the decrease of molecular weight of nylon-6. The motion of molecular chain of the copolymers was easy because of the decreased hydrogen bonds and weakened inter-molecular forces. The physical entanglement of molecular chains of the copolymers was significant and strong which increased the entanglement density. Only the nylon-6 phase crystallized in the copolymers and the crystal grain size, spherulite size and crystallinity of the copolymers decreased. A small amount of γ crystal formed at high polyether amine content. The copolymers presented obvious strain hardening behavior in stress-strain curves and the loss factor dramatically increased while the glass transition temperature and storage module decreased. The fracture surface of the copolymers became rough and presented hairy structure, indicating that the toughening mechanism of the copolymers corresponded to the multi-layer crack extension mechanism.     

Remarkably enhanced energy storage properties of lead-free Ba0.53Sr0.47TiO3 thin films capacitors by optimizing bottom electrode thickness

The lead-free Ba_0.53Sr_0.47TiO₃ (BST) thin films buffered with La_0.67Sr_0.33MnO₃ (LSMO) bottom electrode of different thicknesses were fabricated by pulsed laser deposition method on a (001) SrTiO₃ substrate. It was found that the roughness of electrode decreases and substrate stress relaxes gradually with the increase of LSMO thickness, which is beneficial for weakening local high electric field and achieving higher E_b. Therefore, the recoverable energy density (W_rec) of BST films can be greatly improved up to 67.3 %, that is, from 30.6 J/cm³ for the LSMO thickness of 30 nm up to 51.2 J/cm³ for the LSMO thickness of 140 nm after optimizing the LSMO thickness. Furthermore, the thin film capacitor with a 140 nm LSMO bottom electrode shows an outstanding thermal stability from 20 °C to 160 °C and superior fatigue resistance after 10⁸ electrical cycles with only a slightly decrease of W_rec below 1.6 % and 3.7 %, respectively. Our work demonstrates that optimizing bottom electrodes thickness is a promising way for enhancing energy storage properties of thin-film capacitors.