Good dielectric performance and broadband dielectric polarization in Ag,Nb co-doped TiO2

Due to the demand of miniaturization and integration for ceramic capacitors in electronic components market, TiO₂-based ceramics with colossal permittivity has become a research hotspot in recent years. In this work, we report that Ag⁺/Nb⁵⁺ co-doped (Ag_1/4Nb_3/4)_xTi_1−xO₂ (ANTOx) ceramics with colossal permittivity over a wide frequency and temperature range were successfully prepared by a traditional solid–state method. Notably, compositions of ANTO0.005 and ANTO0.01 respectively exhibit both low dielectric loss (0.040 and 0.050 at 1 kHz), high dielectric permittivity (9.2 × 10³ and 1.6 × 10⁴ at 1 kHz), and good thermal stability, which satisfy the requirements for the temperature range of application of X9R and X8R ceramic capacitors, respectively. The origin of the dielectric behavior was attributed to five dielectric relaxation phenomena, i.e., localized carriers' hopping, electron–pinned defect–dipoles, interfacial polarization, and oxygen vacancies ionization and diffusion, as suggested by dielectric temperature spectra and valence state analysis via XPS; wherein, electron-pinned defect–dipoles and internal barrier layer capacitance are believed to be the main causes for the giant dielectric permittivity in ANTOx ceramics.     

Optimization of hydrogen enrichment via palladium membrane in vacuum environments using Taguchi method and normalized regression analysis

In this study, the separation of hydrogen from gas mixtures using a palladium membrane coupled with a vacuum environment on the permeate side was studied experimentally. The gas mixtures composed of H₂, N₂, and CO₂ were used as the feed. Hydrogen permeation fluxes were measured with membrane operating temperature in the range of 320–380 °C, pressures on the retentate side in the range of 2–5 atm, and vacuum pressures on the permeate side in the range of 15–51 kPa. The Taguchi method was used to design the operating conditions for the experiments based on an orthogonal array. Using the measured H₂ permeation fluxes from the Taguchi approach, the stepwise regression analysis was also employed for establishing the prediction models of H₂ permeation flux, followed by the analysis of variance (ANOVA) to identify the significance and suitability of operating conditions. Based on both the Taguchi approach and ANOVA, the H₂ permeation flux was mostly affected by the gas mixture composition, followed by the retentate side pressure, the vacuum degree, and the membrane temperature. The predicted optimal operating conditions were the gas mixture with 75% H₂ and 25% N₂, the membrane temperature of 320 °C, the retentate side pressure of 5 atm, and the vacuum degree of 51 kPa. Under these conditions, the H₂ permeation flux was 0.185 mol s^?1 m^?2. A second-order normalized regression model with a relative error of less than 7% was obtained based on the measured H₂ permeation flux.     

Recent progress of electrocatalysts for hydrogen proton exchange membrane fuel cells

Due to stringent environmental regulations and the limited resources of fossil-based fuels, there is an urgent demand for clean and eco-friendly energy conversion devices. These criteria appear to be met by hydrogen proton exchange membrane fuel cells (PEMFCs). PEMFCs have attracted tremendous attention on account of their excellent performance with tunable operability and good portability. Nonetheless, their practical applications are hugely influenced by the scarcity and high cost of platinum (Pt) used as electrocatalysts at both cathode and anode. Pt is also susceptible to easy catalyst poisoning. Herein, this paper reviews the progress of the research regarding the development of electrocatalysts practically used in hydrogen PEMFCs, where the corner-stone reactions are cathodic oxygen reduction reaction (ORR) and anodic hydrogen oxidation reaction (HOR). To reduce the costs of PEMFCs, lessening or eliminating the use of Pt is of prime importance. For current and forthcoming laboratory/large-scale PEMFCs, there is much interest in developing substitute catalysts based on cheaper materials. As such are non-platinum (non-Pt), non-platinum group metals (non-PGMs), metal oxides, and non-metal electrocatalysts. Hence, high-performance, state-of-the-art, and novel structured electrocatalysts as replacements for Pt are needed.     

Comb-shaped sulfonated poly(aryl ether sulfone) proton exchange membrane for fuel cell applications

Structure design is the primary strategy to acquire suitable ionomers for preparing proton exchange membranes (PEMs) with excellent performance. A series of comb-shaped sulfonated fluorinated poly(aryl ether sulfone) (SPFAES) membranes are prepared from sulfonated fluorinated poly(aryl ether sulfone) polymer (SPFAE) and sulfonated poly(aryl ether sulfone) oligomer (SPAES-Oligomer). Chemical structures of the comb-shaped membranes are verified by ¹H nuclear magnetic resonance (NMR) and Fourier transform infrared (FT-IR) spectra. The comb-shaped SPFAES membranes display more continuous hydrophilic domains for ion transfer, because the abundant cations and flexible side-chains structure possess higher mobility and hydrophilicity, which show significantly improved proton conductivity, physicochemical stability, mechanical property compared to the linear SPFAE membranes. In a H₂/O₂ single-cell test, the SPFAES-1.77 membrane achieves a higher power density of 699.3 mW/cm² in comparison with Nafion® 112 (618.0 mW/cm²) at 80 °C and 100% relative humidity. This work offers a promising example for the synthesis of highly branched polymers with flexible comb-shaped side chains for high-performance PEMs.     

Mechanical properties,corrosion resistance,and rubber pad forming of cold differential speed-rolled pure titanium for bipolar plates of proton-exchange membrane fuel cells

Due to problems such as pores on surface-treated coatings, the corrosion resistance of pure titanium bipolar plates for proton-exchange membrane fuel cells can be further improved by increasing the corrosion resistance of pure titanium by using differential speed-rolling (DSR); however, these materials have not yet reached the standard requirements of bipolar plates (corrosion current density i_corr＜10³ nA·cm^?2). In this work, the corrosion resistance of pure titanium was improved by optimizing the DSR process while the strength was maintained. The best corrosion resistance of the DSR pure titanium was achieved when the roller speed ratio was 2, while i_corr was 429 nA·cm^?2 in a solution of 0.5 M H₂SO₄ and 2 mg/L HF at room temperature. The formability of the DSR pure titanium for bipolar plates was verified. The optimal holding pressure range was 6.8–7.0 kN.     

Effect of micro-cracks on the in-plane electronic conductivity of proton exchange membrane fuel cell catalyst layers based on lattice Boltzmann method

Micro-cracks commonly occur on the catalyst layers (CLs) during the manufacturing of catalyst coated membranes (CCMs). However, the crack shape parameters effect on CLs in-plane (IP) electronic conductivity λ_s is not clear. In this work, the relationship between crack parameters and the λ_s is obtained based on the two-dimensional (2D) multiple-relaxation time (MRT) lattice Boltzmann method (LBM). The LBM numerical model is validated by the normalized λ_s experiment applied on three different home-made cracked CLs, and the parameter study focus on crack width, length, quantity and phase angle are carried out. The results show that the decrease of λ_s has different sensitivity |k| to the parameters above. The crack width has little effect on λ_s decrease, and the |k_w| is 0.038. However, crack arm length and quantity show more significant impact, which |k_l| and |k_N| are 0.753 and 0.725, respectively. The CLs with different crack propagation directions show significant anisotropy on λ_s, and a 53.53% decrease in λ_s is observed between 0° and 90° crack phase angle change. To manufacture a high electronic conductivity CL, crack initiation and migration mitigation are highly encouraged.     

Analysis and proposition of limiting current density measurement protocol

Limiting current density at different temperatures, backpressures, and balance gases can be used to separate molecular diffusion resistance, Knudsen diffusion resistance and local transport resistance of membrane electrode assembly (MEA). However, the measurement of limiting current density has no unified protocol. The diverse choices in the literature, either in the control of current or voltage or in the atmosphere like relative humidity and O₂ concentrations, make it difficult to compare the results and identify the true bottleneck hindering the mass transport. In this work, the current-voltage curves obtained by current scanning/stepping and voltage scanning/stepping methods under dilute O₂ of different concentrations and a wide range of relative humidity were measured and analyzed systematically. It is found that the voltage stepping method is superior to the other three ways of control for the reliable determination of the limiting current density. Aided with simultaneous electrochemical impedance spectroscopy measurement, the limiting current density can be determined with pinpoint accuracy. When the limiting current density is just used to qualitatively evaluate different MEA, the voltage scanning method can be used instead for its high time efficiency. The selection of the atmosphere also plays an important role in suppressing the distortion from excessive water and reducing the spurious contribution from proton conduction resistance. It is found that O₂ concentrations at 0.5 vol% and relative humidity at 90% can give the best estimation of O₂ transport resistance in membrane electrode assembly.     

SLM printing of cermet powders: Inhomogeneity from atomic scale to microstructure

It is very challenging for 3D printing based on the selective laser melting (SLM) technology to obtain cermet bulk materials with high density and homogeneous microstructures. In this work, the SLM process of the cermet powders was studied by both simulations and experiments using the WC-Co cemented carbides as an example. The results indicated that the evolution of the ceramic and metallic phases in the cermet particle during the heating, melting and solidification processes were all significantly inhomogeneous from atomic scale to mesoscale microstructures. As a consequence, the microstructural defects were caused intrinsically in the printed bulk material. The formation and growth of the bonding necks between the particles were mainly completed at the later stage of laser heating and the early stage of solidification. Both simulations and experiments demonstrated that thin amorphous layers formed at the ceramics/metal interfaces. This work disclosed the mechanisms for the evolution from the atomic scale to microstructure during the SLM printing of cermet powders, and discovered the origin of the defects in the printed cermet bulk materials.     

An adaptive sliding mode observer based near-optimal OER tracking control approach for PEMFC under dynamic operation condition

Tracking control of oxygen excess ratio (OER) is crucial for dynamic performance and operating efficiency of the proton exchange membrane fuel cell (PEMFC). OER tracking errors and overshoots under dynamic load limit the PEMFC output power performance, and also could lead oxygen starvation which seriously affect the life of PEMFC. To solve this problem, an adaptive sliding mode observer based near-optimal OER tracking control approach is proposed in this paper. According to real time load demand, a dynamic OER optimization strategy is designed to obtain an optimal OER. A nonlinear system model based near-optimal controller is designed to minimize the OER tracking error under variable operation condition of PEMFC. An adaptive sliding mode observer is utilized to estimate the uncertain parameters of the PEMFC air supply system and update parameters in near-optimal controller. The proposed control approach is implemented in OER tracking experiments based on air supply system of a 5 kW PEMFC test platform. The experiment results are analyzed and demonstrate the efficacy of the proposed control approach under load changes, external disturbances and parameter uncertainties of PEFMC system.