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.     

Modulation of electrical transport in calcium cobaltite ceramics and thick films through microstructure control and doping

Ca₃Co₄O₉ is a promising p-type thermoelectric oxide material having intrinsically low thermal conductivity. With low cost and opportunities for automatic large scale production, thick film technologies offer considerable potential for a new generation of micro-sized thermoelectric coolers or generators. Here, based on the chemical composition optimized by traditional solid state reaction for bulk samples, we present a viable approach to modulating the electrical transport properties of screen-printed calcium cobaltite thick films through control of the microstructural evolution by optimized heat-treatment. XRD and TEM analysis confirmed the formation of high-quality calcium cobaltite grains. By creating 2.0 at% cobalt deficiency in Ca_2.7Bi_0.3Co₄O_9+δ, the pressureless sintered ceramics reached the highest power factor of 98.0 μWm^?1 K^-2 at 823 K, through enhancement of electrical conductivity by reduction of poorly conducting secondary phases. Subsequently, textured thick films of Ca_2.7Bi_0.3Co_3.92O_9+δ were efficiently tailored by controlling the sintering temperature and holding time. Optimized Ca_2.7Bi_0.3Co_3.92O_9+δ thick films sintered at 1203 K for 8 h exhibited the maximum power factor of 55.5 μWm^?1 K^-2 at 673 K through microstructure control.     

Diluted chemical bath deposition of CdZnS as prospective buffer layer in CIGS solar cell

In this study, dilute chemical bath deposition technique has been used to deposit CdZnS thin films on soda-lime glass substrates. The structural, morphological, optoelectronic properties of as-grown films have been investigated as a function of different Zn²⁺ precursor concentrations. The X-ray diffractogram of CdS thin-film reveals a peak corresponding to (002) plane with wurtzite structure, and the peak shift has been observed with the increase of the Zn²⁺ concentration upon formation of CdZnS thin film. From morphological studies, it has been revealed that the diluted chemical bath deposition technique provides homogeneous distribution of film on the substrate even at a lower concentration of Zn²⁺. Optical characterization has shown that the transparency of the film is influenced by Zn²⁺ concentration and when the Zn²⁺ concentration is varied from 0 M to 0.0256 M, bandgap values of resulting films range from 2.42 eV to 3.90 eV while. Furthermore, electrical properties have shown that with increasing zinc concentration the resistivity of the film increases. Finally, numerical simulation validates and suggests that CdZnS buffer layer with composition of 0.0032 M Zn²⁺ concentration would be a promising candidate in CIGS solar cell.     

Development of high pressure membraneless alkaline electrolyzer

A technology for cyclic generation of hydrogen and oxygen using electrodes made of variable valency material that does not need the use of separating ion-exchange membranes is presented. The technological solution enables to fabricate electrolyzers for uninterrupted producing high-pressure hydrogen with reduced energy intensity of the production. The total work for compressing 1 m³ of hydrogen and 0.5 m³ of oxygen has been estimated. Results of investigation of influence of discrete supply of DC current to the electrolysis cell, in order to improve the processes of gas evolution and to simplify the power systems of the electrolysis plant, have been considered. There is also considered an electrolysis installation equipped with a thermosorption compressor in which LaNi₅ is used as a hydride-forming compound. The comparative characteristics of the developed electrolyzer and the currently used hydrogen generators are given.     

Large domain-wall currents in epitaxial Au/BiFeO3/SrRuO3 thin-film capacitors with modulated oxygen vacancy and wall densities

Large domain wall (DW) conductivity in an insulating ferroelectric plays an important role in the future nanosensors and nonvolatile memories. However, the wall current was usually too small to drive high-speed memory circuits and other agile nanodevices requiring high output-powers. Here, a large domain-wall current of 67.8 μA in a high on/off ratio of ~4460 was observed in an epitaxial Au/BiFeO₃/SrRuO₃ thin-film capacitor with the minimized oxygen vacancy concentration. The studies from read current-write voltage hysteresis loops and piezo-response force microscope images consistently showed remaining of partially unswitched domains after application of an opposite poling voltage that increased domain wall density and wall current greatly. A theoretical model was proposed to explain the large wall current. According to this model, the domain reversal occurs with the appearance of head-to-head and tail-to-tail 180° domain walls (DWs), resulting in the formation of highly conductive wall paths. As the applied voltage increased, the domain-wall number increased to enhance the on-state current, in agreement with the measurements of current-voltage curves. This work paves a way to modulate DW currents within epitaxial Au/BiFeO₃/SrRuO₃ thin-film capacitors through the optimization of both oxygen vacancy and domain wall densities to achieve large output powers of modern domain-wall nanodevices.     

Photophysical investigation of the formation of defect levels in P doped ZnO thin films

Zinc oxide (ZnO) offers a major disadvantage of asymmetry doping in terms of reliability, stability, and reproducibility of p-type doping, which is the main hindrance in realization of optoelectronic devices. The problem is even more complicated due to formation of various native defects in unintentionally doped n-type ZnO. The realization of p-type conductivity in doped ZnO requires an in-depth understanding of the formation of an effective shallow acceptor, as well as donor-acceptor compensation. Photophysical properties such as photoconductivity along with photoluminescence (PL) studies have unprecedentedly and effectively been utilized in this work to monitor the evolution of various in-gap defects. Phosphorus (P) doped ZnO thin films have been grown by RF magnetron sputtering under various Ar to O₂ gas ratios to investigate the effect of O₂ on the donor-acceptor compensation by comprehensive photoconductivity measurements supported by the PL studies. Initial elemental analyses indicate presence of abundant zinc vacancies (V_Zn) in O-rich ambience. The results predict that P sits in the zinc (Zn) site rather than the oxygen (O) site causing the formation of P_Zn–2V_Zn acceptor-like defects, which compensates the donor defects in P doped ZnO films. Photocurrent spectra uniquely reveal presence of more oxygen vacancies (V_O) defects states in lower O₂ flow, which gets compensated with an increase in the O₂ flow. Successive photocurrent transients indicate probable presence of more V_O in the films grown with lower O₂ flow and more V_Zn in higher O₂ flow. Overall the photosensitivity measurements clearly present that O-rich ambience expedites the formation of acceptor defects which are compensated, thereby lowering the dark current and enhancing the ultraviolet photosensitivity.     

毫米波三维异质异构集成技术的进展与应用

三维异质异构集成技术是实现电子信息系统向着微型化、高效能、高整合、低功耗及低成本方向发展的最重要方法,也是决定信息化平台中微电子和微纳系统领域未来发展的一项核心高技术。文章详细介绍了毫米波频段三维异质异构集成技术的优势、近年来的发展趋势以及面临的挑战。利用硅基MEMS 光敏复合薄膜多层布线工艺可实现异质芯片的低损耗互连,同时三维集成高性能封装滤波器、高辐射效率封装天线等无源元件,还能很好地处理布线间的电磁兼容和芯片间的屏蔽问题。最后介绍了一款新型毫米波三维异质异构集成雷达及其在远距离生命体征探测方面的应用。     

Development of an SFMM/CGO composite electrode with stable electrochemical performance at different oxygen partial pressures

This paper carefully evaluates the electrocatalytic activity of Sr₂FeMo_0.5Mn_0.5O₆ (SFMM) double perovskite as a candidate to substitute the state-of-the-art Ni/YSZ fuel electrode. The electrochemical performance of a 40% SFMM/CGO composite electrode was studied in CO/CO₂ and H₂ with different oxygen partial pressure. Two different cell configurations are prepared at a relatively low temperature of 800 °C to increase the electrochemically active surface area. The cell was supported with a 150 μm 10Sc1CeSZ electrolyte in the first configuration. The cell in the second configuration was made by applying a 400 nm thin 8YSZ layer on 150 μm CGO electrolyte to improve the electrolyte ionic conductivity. Improving catalytic activity with increasing oxygen partial pressure is a key characteristic of the developed electrode. The polarization resistance of about 0.34 and 0.56 Ω cm² at 750 °C in 3%H₂O + H₂ and 60% CO/CO₂ makes this electrode a promising candidate for SOCs application.     

Understanding δ-Bi2O3 fluorite degradation mechanism and related solutions for promising applications in distributed multigeneration

Oxygen selective membrane on the base of cermet δ-Bi₂O₃/Ag with an interpenetrating structure has the maximum potential efficiency of air separation. However, the degradation processes, including the phase degradation of fluorite δ-Bi₂O₃, do not make it possible to create a membrane with the required perfection and durability. In this work, the ordering of oxygen vacancies with the transformation of fluorite into the rhombohedral phase (S.G. R-3) was studied by powder HT XRD in situ at 600 °C on dense Bi_0.78Er_0.2Hf_0.02O_1.51 ceramics. Fast regeneration of disordered fluorite occurs at T = 640–700 °C. The phase degradation of fluorite due to the segregation of dopants at the second stage leads into stable phases - sillenite, tetragonal or rhombohedral phase (S.G. R-3m), depending on the composition of δ-Bi₂O₃. Fast regeneration of fluorite occurs when heated to 820 °C, which is unacceptable for membranes. Analysis of all available data allows us to propose approaches to optimize the composition of δ-Bi₂O₃ and technical solutions for creating durable oxygen selective membranes with promising use in distributed multigeneration. As a result of the analysis, a new solid electrolyte with better parameters was obtained.     

Enhanced strains of Nb-doped BNKT-4ST piezoelectric ceramics via phase boundary and domain design

A strategy that constructs the morphotropic phase boundary and manipulates the domain structure has been used to design the component of 0.96[Bi_0.5(Na_0.84K_0.16)_0.5Ti_(1-x)Nb_xO₃]-0.04SrTiO₃ (BNKT-4ST-100xNb) to enhance the strain properties for actuator application. Non-equivalent Nb⁵⁺ donor doping modulates the phase transition from the mixture of rhombohedral and tetragonal phases to the pseudocubic phase and results in the coexistence of multiple phases. Moreover, the high-resolution TEM confirms the existence of polar nano regions that contribute to the macroscopic relaxor behaviour. The size of the domains is reduced with increasing Nb⁵⁺, resulting in an enhanced relaxor behaviour. The ferroelectric-relaxor transition temperature decreases from 85 to below 30 °C, implying a non-ergodic to ergodic relaxor transition. An improved strain of 0.56% and a giant normalized strain of 1120 pm/V were achieved for BNKT-4ST-1.5Nb, which were attributed to the unique domain structure in which nanodomains are embedded in an undistorted cubic matrix. Ferroelectric, antiferroelectric, and relaxor phases coexist. As the electric field is large enough, a reversible phase transition occurs. Furthermore, good temperature stability was obtained due to the stability of the nanodomains, and no degradation in strains was observed even after 10⁴ cycles, which may originate from the reversible phase transition and dynamic domain wall. The results show that this design strategy offers a reference way to improve the strain behaviour and that BNKT-4ST-100xNb ceramics could be a potential material for high-displacement actuator applications.