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.     

Analysis of suitability of TPP ash-slag waste as materials for hydrogen fuel storage

The current trends in energy were described, the main of which is the use of alternative energy sources, especially hydrogen. The most common methods of hydrogen accumulation were proposed: accumulation of compressed gaseous hydrogen in high-pressure tanks; accumulation of liquid hydrogen in cryogenic tanks; storing hydrogen in a chemically bound state; accumulation of gaseous hydrogen in carriers with a high specific surface area. Based on the combination of advantages and disadvantages, the most promising methods of accumulation were selected: storage of liquid hydrogen and storage of hydrogen in carriers with a high specific surface area. The main requirement for materials for hydrogen storage by these methods was revealed – a high specific surface area. Prospects for the development of waste-free low-emission technologies due to the recycling of secondary raw materials and the development of low-temperature technologies for the synthesis of functional and structural materials were substantiated. The applicability of large-scale ash and slag waste from coal-fired thermal power plants as a raw material for obtaining materials by low-temperature technologies was shown. The traditional ways of using ash and slag waste as a raw material, active additive and filler in the production of cements were described. Modern technologies for the production of innovative materials with a unique set of properties were presented, namely carbon nanotubes, silica aerogel and geopolymer materials. The prospect of using geopolymer matrices as a precursor for the synthesis of a number of materials was described; the most promising type of materials was selected – geopolymer foams, which are mainly used as sorbents for purifying liquids and gases or accumulating target products, as well as heat-insulating materials. The possibility of obtaining products of any shape and size on the basis of geopolymer matrices without high-temperature processing was shown. The special efficiency of the development of the technology of porous granules and powders obtained from a geopolymer precursor using various methods was substantiated. The obtained granules can be used in the following hydrogen storage technologies: direct accumulation of hydrogen in porous granules; creation of insulating layers for liquid hydrogen storage units.     

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.     

Preparation,structural and photocatalytic activity of Sn/Fe co-doped TiO2 nanoparticles by sol-gel method

Pure and Sn/Fe co-doped (0.2 at.% Sn and 0.6 at.% Fe, 0.6 at.% Sn and 0.2 at.% Fe, 1.0 at.% Sn and 1.0 at.% Fe) TiO₂ nanoparticles were synthesized via a sol-gel method and subsequently calcined at different temperatures. Furthermore, the particles were analyzed by TG-DSC, XRD, TEM, HRTEM, EDS, SAED and UV–Vis for investigating the influences of dopant and calcination temperature on the thermal effect, composition, morphology, energy band gap (E_g) and the degradation efficiency of methyl orange (MO) under various light irradiations respectively. Results indicated that Sn/Fe co-doping inhibited the crystallization transformation from anatase to rutile phase of TiO₂ and decreased the E_g. The increased calcination temperature and Sn/Fe co-doped effect brought about the abnormal grain growth of TiO₂ nanoparticles. 0.6 at.% Sn/0.2 at.% Fe and 1.0 at.% Sn/1.0 at.% Fe co-doped TiO₂ nanoparticles presented better photocatalytic performance than pure and 0.2 at.% Sn/0.6 at.% Fe co-doped TiO₂ nanoparticles under visible light irradiation mainly due to the decreased E_g. On the contrary, 0.2 at.% Sn and 0.6 at.% Fe co-doped TiO₂ nanoparticles calcined at 650 °C showed the most excellent photocatalytic performance under UV light irradiation, which was about twice as large as that of pure TiO₂ possibly due to the formed hybrid structure of anatase and rutile phase as well as the h⁺-mediated decomposition pathway.     

Fabrication of alumina ceramics with functional gradient structures by digital light processing 3D printing technology

Alumina ceramics with different unit numbers and gradient modes were prepared by digital light processing (DLP) 3D printing technology. The side length of each functional gradient structure was 10 mm, the porosity ratio was controlled to 70%, and the number of units were (1 × 1 × 1 unit) and (2 × 2 × 2 unit) respectively. The different gradient modes were named FCC, GFCC-1, GFCC-2 and GFCC-3. SEM, XRD, and other characterization methods proved that these gradient structures of alumina ceramics had only α-Al2O3 phase and good surface morphology. The mechanical properties and energy absorption properties of alumina ceramics with different functional gradient structures were studied by compression test. The results show that the gradient structure with 1 × 1 × 1 unit has better mechanical properties and energy absorption properties when the number of units is different. When the number of units is the same, GFCC-2 and GFCC-3 gradient structures have better compressive performance and energy absorption potential than FCC structures. The GFCC-2 gradient structure with 1 × 1 × 1 unit has a maximum compressive strength of 19.62 MPa and a maximum energy absorption value of 2.72 × 105 J/m3. The good performance of such functional gradient structures can provide new ideas for the design of lightweight and compressive energy absorption structures in the future.     

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.     

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.