直接二甲醚燃料电池性能的初步研究

研究了阳极催化剂及电解质膜对直接二甲醚燃料电池(DDFC)性能的影响,并与直接甲醇燃料电池(DMFC)进行了比较.在低电压区,以Pt/C为阳极催化剂的DDFC性能较好;在高电压区,Pt-Ru/C的催化行为更好.DDFC的开路电压随着Nafion膜的增厚而升高,使用Nafion115膜的DDFC最大功率密度为46 mW/cm2.在低电流密度区,DDFC的性能优于DMFC;在高电流密度区,DMFC的性能较好,DDFC的最大功率密度约为相同条件下DMFC的84%     

Performance of a novel dot matrix fuel cell using an inorganic micro‐proton conductor

The power generation properties of a novel dot matrix fuel cell using an inorganic micro‐proton conductor were evaluated in dry gas mixtures of hydrogen and oxygen during room‐temperature operation. The single dot matrix fuel cell was composed of aggregates of micro‐electrolyte dots filling pores arranged in a matrix form on a Teflon or polyimide substrate with Pt/C and Pt catalytic electrodes. Micro‐electrolyte dots were prepared by the sol–gel method using titanium phosphorus oxides as the proton conductive hybrid materials. The open‐circuit voltage of the single cell became higher when using a small dot diameter and achieved a maximum of 500 mV with an electrolyte dot density of 17 dots/cm² in the dry gas mixtures during room‐temperature operation. This value corresponds to about one‐half of the theoretical electromotive force. Moreover, the current density of the single cell increased with the dot diameter such that it grew to 8 mA/cm² at a dot diameter of 500 µm. As a result, dot matrix fuel cells connected in series and parallel were found to achieve the cell performance of high‐energy density such as used by high‐energy microchips. © 2012 Institute of Electrical Engineers of Japan. Published by John Wiley & Sons, Inc.     

Performance of surface ionic conduction single chamber fuel cell prepared by the sol gel method

The performance of surface ionic conduction single chamber fuel cell (SIC‐SCFC) prepared by the sol gel method was studied on electric characteristics due to the differences of the operating temperature and humidity, the electrode distance and electrolyte film depth, and multiple cells with the series and parallel connections. The SIC–SCFC was arranged the both anode of Pt and cathode of Au on the boehmite electrolyte. The open circuit voltage (OCV) of single cell achieved a maximum of 530mV in the dry gas mixtures of O₂/H₂=50% in room temperature operation, and but it became decrease as over 60%. The OCV was maintained the constant value between operating temperatures of 30°C to 80°C, and but it was decreased sharply at over 90°C because a humidity on the cell became lower as increasing operating temperature. Then, the cell property was improved to 120°C by adding to the humidity of 70% using a humidifier. The electrode distance and the electrolyte film depth of SIC‐SCFC found to be contributed to the reductions of the cell resistance and the surface roughness on the electrode, respectively. Moreover, the power property of SIC‐SCFC was significantly improved by cell stacks comprised of the series or parallel connection of a cell.     

Performance of several types of fuel cells and factor analysis of performance

There are four types of fuel cells: Polymer Electrolyte Fuel Cells (PEFC), Phosphoric Acid Fuel Cells (PAFC), Molten Carbonate Fuel Cells (MCFC), and Solid Oxide Fuel Cells (SOFC). The performance of these fuel cells has not been compared. Equations that are able to express the performance of these fuel cells accurately were derived or modified from the latest published performance data. The cell voltages of the four fuel cells were estimated by these equations, resulting in high‐temperature fuel cells such as MCFC and SOFC having higher energy conversion efficiencies than low‐temperature fuel cells such as PEFC and PAFC. This difference originates from low cathode polarization, overcoming both a decrease of open circuit voltage with increasing temperature and higher Nernst losses for high‐temperature fuel cells of approximately 85 mV than those for low‐temperature fuel cells due to steam generation in the anode chamber in the high‐temperature fuel cells. A generalized relationship between cell voltage and operating temperature was derived, stating that the cell voltage is almost constant between 500 °C and 1000 °C. A fuel cell which has protons as a migration species in the electrolyte and works between 250 °C and 500 °C would give a performance comparable with high‐temperature fuel cells due to lower Nernst losses than those for high‐temperature fuel cells. © 2001 Scripta Technica, Electr Eng Jpn, 138(1): 24–33, 2002     

CO对PEMFC性能影响研究

天然气、甲醇等碳氢化合物重整制氢作为燃料正在应用到质子交换膜燃料电池领域。为系统地研究重整气中CO对质子交换膜燃料电池性能的影响,采用热压法自制膜电极,研究了CO浓度、催化剂种类、操作温度、增湿操作等因素对质子交换膜燃料电池性能的影响。实验结果表明:20×10~(-6) CO浓度即能使电池性能显著下降60%~70%;Pt Ru/C催化剂对抗CO中毒的能力较Pt/C催化剂有明显提升,在100×10~(-6) CO浓度下能使性能提高70%;提高工作温度能有效地改善阳极CO中毒状况,在50×10~(-6) CO浓度并加湿的条件下,当操作温度从80℃提高到120℃时电池性能可增加一倍。同时增湿操作有利于改进电池在低浓度CO下的发电性能。     

Alcohol electrooxidation at Pt‐Ru sputter‐deposited electrode

The use of various alcohols including methanol has been considered as the fuel of direct alcohol fuel cells (DAFCs). Thus far, the Pt alloys have mainly been studied as anode electrocatalysts for DAFCs. Pt itself is poisoned by chemical species produced during the alcohol oxidation. There exist many reports that the addition of Ru is effective for alcohol oxidation. In this work, we prepared a Pt‐Ru co‐sputtered electrode by changing the Ru content, sputtering time, and Ar pressure for the sputtering. By using the prepared electrocatalysts, relationships between sputtering conditions and electrocatalytic activity were measured for some alcohols. © 2008 Wiley Periodicals, Inc. Electr Eng Jpn, 163(2): 14–21, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/eej.20594     

Bottom electrode structures of Pt/Ru and Ru deposited on polycrystalline silicon by MOCVD for DRAM capacitor

Abstract

The electrode structures of Pt/Ru and Ru on polycrystalline silicon (poly-Si) were prepared by metalorganic chemical vapor deposition (MOCVD) for high dielectric constant (Ba, Sr)TiO₃(BST) capacitor integration. The electrode structures of Pt/Ru/poly-Si annealed above 700°C for 1h in oxygen atmosphere showed a smooth surface ·microstructure without any second phases on the platinum. The specific contact resistance of Pt/Ru and poly-Si in Pt/Ru/poly-Si structures annealed at 800°C was about 1.5 × 10^?5 Ω-cm². The step coverage of Ru film deposited at 150°C was 76% and those of Pt film deposited at 300°C on Ru (deposited at 150°C) was about 61.3%.     

Characteristics evaluation of a CO2‐capturing power generation system with reheat cycle utilizing regenerative oxygen‐combustion steam‐superheater

A new CO₂‐capturing power generation system is proposed that can be easily realized by applying conventional technologies. In the proposed system, the temperature of medium‐pressure steam in a thermal power plant is raised by utilizing an oxygen‐combusting regenerative steam‐superheater. The CO₂ generated by combusting the fuel in the superheater can be easily separated and captured from the exhaust gas at the condenser outlet, and is liquefied. The superheated steam is used to drive a steam turbine power generation system. Using a high‐efficiency combined cycle power generation system as an example, it is shown that the proposed system can increase the power output by 10.8%, and decrease the CO₂ emissions of the entire integrated system by 18.6% with a power generation efficiency drop of 2.36% compared with the original power plant without CO₂ capture, when the superheated steam temperature is 750 ^°C. © 2008 Wiley Periodicals, Inc. Electr Eng Jpn, 165(1): 35–41, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/eej.20575     

Thermal stability of metal electrodes (Pt,Ru, & Ir) on polycrystalline silicon in ferroelectric capacitors

Abstract

Electrode materials such as Pt, Ru, and Ir on polycrystalline silicon were annealed and the thermal stability was investigated to check the feasibility of the structure. Sputtered Pt reacted with silicon to form PtSi at a low temperature of 400 °C and the top layer of silicide was oxidized in oxygen ambient. Ru and Ir films by sputtering were also silicidized above 550 °C and it made voids beneath silicide layers. All of the films are found to allow oxygen to diffuse through them and to get the underlying layers oxidized. However, Ir deposited by e-beam evaporation did not form silicide up to 700 °C and did not get oxidized up to 550 °C. Ir also allowed oxygen diffusion when annealed at 550 °C or lower temperature, but it was prevented when annealed at 700 °C.     

Methods for maintaining reheat steam temperature at a TPP-110 boiler at lowered loads

Methods for maintaining the temperature of the reheated steam at the TPP-110 twin-furnace boiler of the Novocherkassk GRES during operation at a lowered load are considered. It is shown taht the rated temperature of the steam superheat (545°C) can be ensured down to a boiler load of 40% of the nominal one through the redistribution of fuel and feedwater flowrates between the boiler casings and the delivery of flue gas recirculation in casing B.     

Improvement of heating characteristics of molybdenum silicide thin film electric heaters

Molybdenum silicide (MoSi₂) has an electrical conductivity as high as that of a metal, and greater chemical stability than that of, for example, SiC, in various atmospheres. Therefore, many kinds of MoSi₂ bulk‐type heaters are used in practical operations up to 1800^°C, which is higher than the temperature of SiC heaters. However, MoSi₂ is fragile at room temperature and has low creep resistance at high temperature. The purpose of this study is to fabricate heaters using thin films of MoSi₂ deposited on alumina substrates and crucibles by RF magnetron sputtering and to evaluate their characteristics. MoSi₂ thin film was deposited on the outside of an alumina crucible without heating the substrate and then Pt wire was attached using a Pt paste with sintering in a vacuum. This MoSi₂ thin film heater showed almost linear resistance–temperature (R–T) characteristics and a uniform heating state. It also showed good controllability of voltage and stability in the power–T characteristics for operations up to 1000^°C. However, at a heating temperature of 1300^°C, the heating area of MoSi₂ thin film decreased because of the reaction between Pt and MoSi₂ in the case of long‐term heating. Thus, Mo thin film was deposited as a buffer layer between Pt and MoSi₂ thin film to prevent such a reaction. This thin film heater showed good linear R–T characteristics up to 1200^°C. However, the temperature coefficient of resistance changed with repeated heating operation as a result of the diffusion of Mo atoms into MoSi₂. Thus, a thin film heater was fabricated with Mo₃Si, having a higher Mo content than MoSi₂. This heater showed a low degree of diffusion of Mo or Pt atoms into the thin film and had excellent practical characteristics up to 1000^°C. © 2009 Wiley Periodicals, Inc. Electr Eng Jpn, 168(2): 11–19, 2009; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/eej.20806     

Chemical Vapor Deposition of Ru Bottom Electrode for Ferroelectric Bi4 − x La x Ti3O12 Capacitors

Ruthenium films formed by metalorganic chemical vapor deposition were investigated, taking account of the application to the bottom electrode of ferroelectric capacitors. Ruthenium films were deposited using a liquid-type source of Ru[EtCp]₂ in a cold-wall type reactor with infrared lamps. A smooth and flat Ru film was successfully formed on a SiO₂-covered Si substrate without a seed layer. As the deposition temperature increased to 400°C, the crystallinity of the Ru film improved and the film exhibited high c-axis orientation. After forming a Bi_{4 ? x} La _x Ti₃O₁₂ (BLT) film by a sol-gel technique, a Pt/BLT/Ru capacitor was fabricated on the Ru film. Good hysteresis loops with 2P _r = 20 μC/cm² and 2V _c = 3.4 V were successfully obtained and the ferroelectric property did not depend on the deposition temperature of Ru in the temperature range from 325°C to 400°C. On the contrary, the leakage current density was significantly suppressed down to 1/100 as the deposition temperature of Ru increased from 325°C to 400°C.     

Combined cycle plants: Yesterday,today, and tomorrow (review)

Gas turbine plants (GTP) for a long time have been developed by means of increasing the initial gas temperature and improvement of the turbo-machines aerodynamics and the efficiency of the critical components air cooling within the framework of a simple thermodynamic cycle. The application of watercooling systems that were used in experimental turbines and studied approximately 50 years ago revealed the fundamental difficulties that prevented the practical implementation of such systems in the industrial GTPs. The steam cooling researches have developed more substantially. The 300 MW power GTPs with a closedloop steam cooling, connected in parallel with the intermediate steam heating line in the steam cycle of the combined cycle plant (CCP) have been built, tested, and put into operation. The designs and cycle arrangements of such GTPs and entire combined cycle steam plants have become substantially more complicated without significant economic benefits. As a result, the steam cooling of gas turbines has not become widespread. The cycles—complicated by the intermediate air cooling under compression and reheat of the combustion products under expansion and their heat recovery to raise the combustion chamber entry temperature of the air—were used, in particular, in the domestic power GTPs with a moderate (700–800°C) initial gas turbine entry temperature. At the temperatures being reached to date (1300–1450°C), only one company, Alstom, applies in their 240–300 MW GTPs the recycled fuel cycle under expansion of gases in the turbine. Although these GTPs are reliable, there are no significant advantages in terms of their economy. To make a forecast of the further improvement of power GTPs, a brief review and assessment of the water cooling and steam cooling of hot components and complication of the GTP cycle by the recycling of fuel under expansion of gases in the turbine has been made. It is quite likely in the long term to reach the efficiency for the traditional GTPs of approximately 43% and 63% for PGUs at the initial gas temperature of 1600°C and less likely to increase the efficiency of these plants up to 45% and 65% by increasing the gas temperature up to 1700°C or by application of the steam cooling in the recycled fuel cycle.     

A 0.7 V, 2.7 μW, 12.9 ppm/° C over 180° C CMOS subthreshold voltage reference

An all‐CMOS, low‐power, wide‐temperature‐range, curvature‐compensated voltage reference is presented. The proposed topology achieves a measured temperature coefficient of 12.9 ppm/°C for a wide temperature range of 180°C ( − 60 to 120°C) at a bias voltage of 0.7 V while consuming a mere 2.7 μW. The high‐order curvature compensation, which leads to a low‐temperature sensitivity of the reference voltage, is performed using a new, simple, but efficient methodology. The non‐linearities of an N‐type metal‐oxide‐semiconductor (NMOS) device operated in subthreshold are combined with the non‐linearities of two different kinds of polysilicon resistors, leading to the improved performance. The extended temperature range of this voltage reference gives it an important competitive advantage, especially at lower temperatures, where prior art designs' performance deteriorate abruptly. In addition, it utilizes an innovative trimming methodology whereby two trimmable resistors enable the tuning of both the overall slope and non‐linearities of the temperature sensitivity. The design was fabricated using TowerJazz Semiconductor's CMOS 0.18 μm technology, without using diodes or any external components such as compensating capacitors. It has an area of 0.023 mm² and is suitable for high‐performance power‐aware applications as well as applications operating in extreme temperatures. Copyright © 2016 John Wiley & Sons, Ltd.     

Proposal and characteristics evaluation of a CO2-recovering hybrid power generation system utilizing solar thermal energy

A CO₂-recovering hybrid power generation system utilizing solar thermal energy is proposed. In the system, relatively low temperature saturated steam around 220°C is produced by using solar thermal energy and is utilized as the working fluid of a gas turbine in which generated CO₂ is recovered based on the oxygen combustion method. Hence, solar thermal utilization efficiency is considerably higher as compared with that of conventional solar thermal power plants in which superheated steam near 400°C must be produced for use as the working fluid of steam turbines; the requirement for solar radiation in the location in which the system is constructed can be significantly relaxed. The proposed system is a hybrid energy system using both the fossil fuel and solar thermal energy, thus the capacity factor of the system becomes very high. The fuel can be used exergetically in the system; i.e., it can be utilized for raising the temperature of the steam heated by utilizing the turbine exhaust gas more than 1000°C. The generated CO₂ can be recovered by using an oxygen combustion method, so that a high CO₂ capturing ratio of near 100 percent as well as no thermal NO_x emission characteristics can be attained. It has been shown through simulation study that the proposed system has a net power generation efficiency of 63.4 percent, which is higher than 45.7 percent as compared with that of the conventional power plant with 43.5 percent efficiency, when the amount of utilized solar energy is neglected and the temperature of the saturated steam is 220°C.     

Improvement of anode oxidation reaction of a fuel cell using ammonium formate with Pt‐Ir catalysis

We have attempted to develop high‐performance and safe fuel cells by using ammonium formate as a solid (powder) fuel. This solid fuel has the potential of safer transportability than liquid fuels such as methanol from the viewpoint of toxicity and flammability. In order to make use of some of the advantages of ammonium formate, we investigated the oxidation characteristics of ammonium formate with respect to a Pt electrode. Cyclic voltammograms indicate that ammonium formate has high oxidation activity with respect to a Pt electrode. We have also found that the oxidation of ammonium formate can be improved by the addition of Ir to Pt catalysts. It is highly likely that ammonium formate will be useful as a solid (powder) fuel for polymer electrolyte membrane (PEM) fuel cells. This new fuel will promote the development of safe fuel cells for PEM. © 2010 Wiley Periodicals, Inc. Electr Eng Jpn, 174(4): 45–50, 2011; Published online in Wiley Online Library ( wileyonlinelibrary.com ). DOI 10.1002/eej.21043     

Effects of different morphologies of ZnO films on hydrogen sensing properties

This paper describes the characteristics of chemiresistor hydrogen (H₂) sensors with different ZnO film structures in which ZnO dense films, nanoparticles (NPs), and nanorods (NRs) were prepared by RF magnetron sputtering, the sol–gel method, and the hydrothermal method, respectively. These were decorated with a Pt NP catalyst to investigate the performance of devices comprised of these structures. The effects of the ZnO morphology and operating temperature on the gas sensing behavior of the sensor are reported in detail. The various ZnO film morphologies, which contributed significantly to differences between sensors, play a very important role in enhancement of the supported Pt catalyst area and initial oxygen absorption on the ZnO surface. ZnO dense films prepared by sputtering showed the fastest response with a 13.5 % resistance variation at 1,000 ppm H₂ because gas adsorption occurred only on the film surface. The sensor with ZnO NRs showed a slower response, but the highest change in resistance of 65.5 % occurred at 1,000 ppm H₂ at room temperature. H₂ sensing performance of the chemiresistor sensors was improved due to the Pt catalyst, which was more efficient in dissociating H₂ gas molecules even at low temperature. The best chemiresistor sensor was fabricated using ZnO NRs and had a response time of approximately 10 s, a 27 s recovery time, and an 81.5 % change in resistance at 200 °C.     

质子交换膜燃料电池Pt/C催化剂的回收再利用

回收质子交换膜燃料电池(PEMFC)失效的Pt/C催化剂,通过高温灼烧得到贵金属Pt渣。Pt渣经适量王水溶解、煮沸、浓缩和再稀释制成H2PtCl6溶液。以H2PtCl6为Pt的前驱体,采用无机胶体法重新制备出PEMFC用Pt/C催化剂。透射电子显微镜测试结果表明,采用优化的工艺条件所制备的Pt/C催化剂平均粒径为2.6nm,且分散性好、粒度均匀。X射线衍射分析表明,催化剂中Pt(111)晶面的相对含量较高,其面间距较小,且催化剂的结晶度略有降低,这些结构特点对催化氧还原反应是有利的。循环伏安法测试表明所制备的Pt/C催化剂对氢和氧电极过程具有良好的电催化性能。     

A 9‐bit successive approximation ADC in SOI CMOS operating up to 300 °C

Industrial electronics are in great demand for oil and gas exploration, well drilling, and automotive applications where the operating temperature goes beyond 200 °C. Circuit designs using conventional complementary metal–oxide semiconductor (CMOS) technology are mostly rated at maximum of 125 °C, which is not suitable for harsh environment. In this paper, a high‐temperature (HT) 9‐bit successive approximation register analog‐to‐digital converter (SAR ADC) designed in silicon‐on‐insolation CMOS technology with a sampling rate of 50 kS/s is presented. The design considerations of the HT SAR ADC are discussed from process selection, temperature‐aware circuit design, and measurement perspectives. The ADC achieves an effective number of bit (ENOB) of 8.35 bits and a figure of merit of 93 pJ/step at room temperature. Under HT test, ENOBs of 7.3 bits at 225 °C and 6.9 bits at 300 °C are obtained. The power consumption is 1.52 mW from a 5‐V supply at room temperature and only 2.17 mW at 300 °C. Copyright © 2015 John Wiley & Sons, Ltd.     

Construction and power generation characteristics of H2O turbine power generation system utilizing waste heat from factories

A new gas turbine power generation system has been proposed, in which the steam (H₂O) produced by utilizing waste heat from factories is used as the working fluid of gas turbine. A simulation model has been constructed to estimate power generation characteristics of the proposed system by adopting C++ language. It has been shown from simulation results that the proposed system has high exergetic efficiency, that is, the total exergetic efficiency is 46.3% and fuel‐based efficiency is 56.3% for a case where steam with a temperature of 275 °C produced from a garbage incineration plant is used. Sensitivity analysis has also been carried out when usable steam temperature and pressure is changed, together with the case when condenser outlet pressure is changed. Characteristics of a dual fluid gas turbine cycle power generation system (DFGT) have also been estimated in this study. It has been shown that the proposed system has 16.9% higher exergetic efficiency and 41.8% higher fuel‐base exergetic efficiency compared with DFGT. © 1999 Scripta Technica, Electr Eng Jpn, 130(1): 38–47, 2000