低温太阳热与甲醇化学链整合能量释放机理实验初探

本文在低温太阳热能与CH3OH-Fe2O3化学链燃烧相结合控制CO2分离动力系统的基础上,进一步探讨了低温太阳热能品位提升的内在规律,分别揭示出辐照强度与CH3OH-Fe2O3反应特性、低温太阳热能品位提升的关联关系.本文采用溶胶凝胶法制作了Fe2O3反应颗粒,在热重反应器中进行了模拟太阳热能与甲醇化学链实验的初步研究,通过电镜,分析了反应前后金属氧化物的表面形貌特征.研究成果将为低温太阳热能与化学链燃烧整合能量释放新机理的研究提供理论依据和基础实验数据.     

低温太阳热能与化学链燃烧相结合控制CO2分离动力系统

本文探索并提出控制CO2分离的低温太阳热能与清洁合成燃料甲醇-三氧化二铁化学链燃烧相结合的新颖能源动力系统。基于图象(?)分析方法,明确地指出甲醇化学链燃烧能量释放过程燃烧堋损失减小和低温太阳热能品位提升的机理。从能源有效利用和环境相容出发,研究和揭示化学链燃烧与太阳能有机整合共同减小CO2分离能耗的特性规律。相比不分离常规联合循环,新系统(?)效率提高约6．2个百分点;与分离CO2的联合循环相比,新系统媚效率提高约14．2个百分点。同时,低温太阳热能热转功效率可达到22．5％。     

基于甲醇化学链燃烧的新型燃气轮机间冷循环

本文提出一种新颖的甲醇化学链燃烧动力循环系统.该系统利用空气压缩的间冷热提供甲醇和Fe2O3反应热,将间冷的低温热转换为高品位化学能;同时得到预冷的空气吸收燃烧产物Fe2O3的显热,降低了还原反应的温度.与常规化学链循环相比,该循环利用间冷的热量代替高温Fe2O3的显热提供还原反应的反应热,系统内能量品位匹配更加合理.根据图像(火用)分析方法,阐明了甲醇化学链燃烧过程(火用)损失减少和间冷热品位提升的机理.本文对新循环进行了分析,并以常规化学链循环为参照,研究了其性能.新循环的效率较高,同时可以实现CO2无能耗的分离.     

中温太阳能驱动甲烷化学链重整冷热电系统及性能研究

针对高温太阳能与天然气热化学互补分布式能源系统存在聚光比高、互补反应温度高、变工况性能不稳定的技术瓶颈,本文探索了一种能实现主动调控的中温太阳能与天然气互补的化学链重整冷热电联产系统。利用约500℃太阳热能驱动天然气基-氧化镍化学链重整,生成合成气太阳能燃料,通过燃气轮机冷热电联产系统,实现中温太阳能与天然气综合梯级利用.研究结果表明:在设计点工况条件下,系统的总能效率可达到80.9%,太阳能集热面积节约率达到53.2%,太阳能净发电效率可达27.3%.分析了关键参数如NiO和甲烷摩尔比(Ni/C)和太阳辐照强度(DNI)对系统热力学性能的影响。     

中低温太阳热能的甲醇重整制氢能量转换机理研究

通过甲醇-水蒸汽化学反应,本文提出中低温太阳热能与甲醇重整反应结合的制氢新方法,探讨了中低温太阳热能与甲醇重整制氢过程的能量转换机理,分析了不同压力条件下的水碳比、反应温度对中低温太阳热能-甲醇重整制氢的影响规律.研究结果表明:集热180～240 ℃的低品位太阳热能(品位为0.34～0.42)将能更好地与甲醇重整反应所需的品位相匹配.在反应压力为1×1.01325×105 Pa,反应产物中H2浓度可有望达到72%～75%,中低温太阳热能转化为化学能占燃料化学能的份额可达12%.该研究为低能耗制取清洁燃料氢提供了一条新途径.     

太阳能甲醇分解能量转换机理实验研究

本文通过太阳能分解甲醇燃料实验,来研究太阳能与化石燃料互补的能源利用系统的能量转换新机理,揭示减少燃料化学能释放过程(火用)损失和提升太阳热能品位的本质,并得到基于实验的量化依据。实验研究了反应过程能量品位关联机理和效果,并揭示了主要因素影响规律。太阳热能温度的升高,有利于分解反应的进行,但温度过高会负面影响品位提升的效果,260℃左右是较合理的;与太阳能甲醇分解反应装置规模对应的进料量条件是影响能量转换过程的关键因素,也将影响太阳热能品位提升效果。研究成果将为开拓太阳能与化石能源互补的能量系统提供理论支撑和实验数据。     

物质系统的和的统一表达式

文献[1]指出,在物质流的能量方程中,pv这一项不是物质所携有的一种能量(流动能),而是克服压力所作的流动功.但是现有的物质系统的(火用)和(火无)的计算公式(例如文献[2])中,仍然将pv这一项视为物质流所携有的一种能量.文献[3]得到了一个(火用)和(火无)的统一公式.但是文献[3]将pv这一项视为环境功l_am.还有,文献[3]的(火无)的统一公式中不包括u_am,这也是不合理的.     

太阳能与LNG冷能耦合发电系统研究

基于能的梯级利用和品位提升原理,本文提出一种耦合太阳能和LNG冷能应用的新型燃气-氨水联合循环发电系统。该系统将中低温太阳热能间接转化为高品质电能,以氨水作为朗肯循环工质,并最大化地利用LNG冷能。从系统性能和节能潜力出发,该系统热力学第一定律效率达65%~75%,系统(火用)效率达56%~64%,均远高于常规天然气基联合循环,而引入中低温太阳热能、高温燃气新途径利用、氨水工质朗肯循环以及LNG冷能应用是系统性能提高的关键过程。本文为化石能源和可再生能源的综合互补应用提供了新思路。     

太阳能与甲醇热化学互补的分布式能源系统研究

本文提出一种基于中低温太阳能与甲醇热化学互补的分布式冷热电供能系统。基于热力学基本定律,对系统作了能量平衡分析和(火用)平衡分析,探讨了变太阳辐照下系统的热力性能和储气蓄能的变化特性规律。结果表明:设计工况下,系统的一次能源效率达89.36%,(火用)效率达到47.10%,太阳直射辐照强度从500 W/m~2变化到900 W/m~2时,系统一次能源效率和冷、热、电功率输出保持稳定。本文的研究成果为高效利用中低温太阳能热化学技术与分布式冷热电能源系统集成技术提供了新途径。     

化学能梯级利用机理探讨

本文提出化学能梯级利用新概念,从理论上证明了物质作功能力(ε)、化学反应作功能力(G)和物理能作功能力(ηc)之间的内在联系,拓展了传统热力循环在物理能转换利用范畴的局限。通过CH4直接燃烧和化学链燃烧化学能品位和(火用)损失的比较,指明化学能梯级利用是降低燃烧(火用)损失的有效途径,并指出影响化学能梯级利用的关键因素,揭示了化学能梯级利用机理。     

Phosphorus-based nanothermites: A new generation of energetic materials

Thermites are energetic materials that are classically made of a transition metal oxide mixed with a reducing metal. Contrary to explosives, thermites do not detonate because their combustion is relatively slow and their reaction by-products are often solid or liquid. The use of nanoparticles to prepare superthermites is very promising. The dramatic changes observed in their reactivity were reported by numerous recent papers dealing with the use of aluminium as fuel.Red phosphorus is widely used in pyrotechnic devices. Highly explosive compositions are classically obtained by mixing this substance with strong oxidizers such as oxygenated potassium salts (chlorate, nitrate). But to our knowledge, the idea to prepare P-nanothermites with metallic oxide nanoparticles was never reported before. In order to illustrate this new concept of energetic formulations, P-nanothermites were prepared from nickel oxide (NiO), iron oxide (Fe₂O₃), and copper oxide (CuO) nanopowders. The reactivity of these compositions was studied by thermogravimetric analysis, impact and friction tests, electrostatic discharge and high-speed cinematography. P-nanothermites are very insensitive to thermal and impact stress. Their combustion rates strongly depend on the nature of the oxide (NiO <Fe₂O₃?CuO). The SEM observation of the microstructure of the residues produced by the combustion clearly indicates that they were formed by the solidification of molten phases. In other words, the energy released by the combustion of P-nanothermites provokes the melting of the reaction products. The temperatures reached are thus high enough to cause the gasification of phosphoric anhydride produced by the combustion. For this reason, P-nanothermites can be considered gas-generating materials.     

Initial stages of hydrogen reduction of NiO(100)

The reduction of single crystal NiO(100) under hydrogen has been followed by AES, XPS and LEED for the pressure range of 1.0 × 10^?7 to 1.3 × 10^?6 Torr and for substrate temperatures of 150–350°C. The kinetics of reduction are controlled both by the rate of removal of lattice oxide at the surface and by the diffusion of subsurface oxygen to the oxygen-depleted surface. The rate of oxygen removal is first-order in surface oxide concentration and in hydrogen pressure. An induction period precedes the reduction reaction and its length is postulated to be controlled by surface defect concentration. The stoichiometric and reduced lattice oxygen species appear to be chemically identical and give a single symmetric XPS peak at 529.4 eV. Nickel spectra indicate a shift in XPS binding energies from those expected of the oxide to those of nickel metal early in the reduction process, although LEED indicates the NiO(100) surface lattice to remain the stable structure for surface reduced to approximately 20% of the stoichiometric oxygen concentration. Ni(100) island formation is observed, with Ni 〈010〉 and 〈001〉 directions along the NiO 〈010〉 and 〈001〉, respectively, but only after the NiO surface is severely depleted in oxygen.     

Ultrathin nickel oxide film as a hole buffer layer to enhance the optoelectronic performance of a polymer light-emitting diode

In order to promote a polymer LED (PLED), we fabricated and introduced an ultrathin nickel oxide (NiO) buffer layer (<10 nm) between the indium tin oxide (ITO) anode and the poly (3, 4-ethylenedioxythiophene) hole injection layer in the PLED. The NiO buffer layer was easily formed on the ITO anode by electron-beam deposition of a nickel (Ni) metal source and an oxygen plasma treatment process. As a result, the PLED device with the NiO buffer layer on its ITO anode had the same turn-on voltage as conventional PLED devices without the NiO buffer layer, and the luminance of the PLED device with the NiO buffer layer was doubled, compared with the conventional PLED devices without the NiO buffer layer. Improvement of the optoelectronic performance of the PLED can be attributed to the increase of the current driven into the diode, resulting from the NiO buffer layer, which can enhance the hole injection and balance the injection of the two types of carriers (holes and electrons). Thus it is an excellent choice to introduce the NiO buffer layer onto the ITO anode of the PLED devices in order to enhance the optoelectronic performance of PLED devices.     

Controlling the infrared optical properties of rf-sputtered NiO films for applications of infrared window

In this paper, we will focus on an IR transmittance enhancement technique from the window material point of view by using metal oxides, especially nickel oxide (NiO). At first, anti-reflection (AR) coatings were modeled by using the optical properties of NiO films. The transmittance of the model was predicted using Swanepoel’s model and verified with NiO film prepared by rf magnetron sputtering. Also, post-deposition annealing was performed and was found to change the optical properties of the NiO film. Therefore, we analyzed the annealing effect on the IR optical properties of the NiO film. Furthermore, we confirmed the durability of the NiO film and verified the possibility of this material being used in infrared optics.     

In situ TEM study of reversible and irreversible electroforming in Pt/Ti:NiO/Pt heterostructures

Experimental verification of the microscopic origin of resistance switching in metal/oxide/metal heterostructures is needed for applications in non‐volatile memory and neuromorphic computing. Numerous reports suggest that resistance switching in NiO is caused by local reduction of the oxide layer into nanoscale conducting filaments, but few reports have shown experimental evidence correlating electroforming with site‐specific changes in composition. We have investigated the mechanisms of reversible and irreversible electroforming in 250–500 nm wide pillars patterned from a single Ta/Ti/Pt/Ti‐doped NiO/Pt/Ta heterostructure and have shown that these can coexist within a single sample. We performed in situ transmission electron microscopy (TEM) electroform‐ ing and switching on each pillar to correlate the local electron transport behavior with microstructure and composition in each pillar. DFT calculations fitted to electron energy loss spectroscopy data showed that the Ti‐doped NiO layer is partially reduced after reversible electroforming, with the formation of oxygen vacancies ordered into lines in the 〈110〉 direction. However, under the same probing conditions, adjacent pillars show irreversible electroforming caused by electromigration of metallic Ta to form a single bridge across the oxide layer. We propose that the different electroforming behaviors are related to microstructural variations across the sample and may lead to switching variability. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Scanning tunneling microscopy imaging of NiO(100)(1 × 1) islands embedded in Ag(100)

The imaging of NiO(100)(1 × 1) islands embedded in Ag(100) by scanning tunneling microscopy is addressed. As a function of tunneling conditions and tip termination it is possible to resolve the NiO–vacuum interface, the second oxide layer as well as the NiO-substrate interface with atomic contrast. We find that for sub-monolayer coverages of NiO the oxide islands consist of an essentially defect-free surface layer at the vacuum interface with a number of NiO second layer patches incorporated into the Ag substrate underneath. The oxide layer is surrounded by a rim of a NiO bilayer of monoatomic width. A reduction of the density of states between a NiO monolayer and local NiO bilayer stackings is suggested to be responsible for the observed appearance of mosaic patches at the island surface.     

The formation of sharp NiO(1 0 0)-cobalt interfaces

An atomically sharp interface between an antiferromagnetic oxide and a ferromagnetic metal may be obtained by the deposition of an epitaxial oxide buffer nanolayer in between. The buffer layer consists of the oxide of the ferromagnetic metal. The concept has been demonstrated on the NiO(1 0 0)-Co system, where the inclusion of a 1-2 ML CoO(1 0 0) interlayer inhibits the interfacial redox reaction which takes place between NiO and Co metal in the absence of the buffer layer.     

Cobalt and tantalum additions for enhanced electrochromic performances of nickel-based oxide thin films grown by pulsed laser deposition

Aiming at improving the durability of anodic electrochromic nickel oxide thin films, Ni-M-O (M = Co, Ta) thin films were grown by pulsed laser deposition (PLD), using optimized conditions, namely room temperature and 10⁻¹ mbar oxygen pressure. For low Co and Ta contents (<5%), both additions lead to a loss of the [1 1 1] preferred orientation of the NiO rock-salt structure followed by a film amorphization with increasing Ta amount. Among the two series of metal additions (M ≤ 20%), the Ni-Co-O (5% Co) and Ni-Ta-O (10% Ta) thin films show the highest electrochemical performances especially in respect of improved durability. If the enhanced properties are associated with a limited dissolution of the oxidized phase for the Ni-Ta-O system, the opposite trend is observed for the Ni-Co-O system as compared to pure NiO.     

Fabrication of hollow thin films of yttria-stabilized zirconia by chemical vapor infiltration using NiO as oxygen source

Deposition of yttria-stabilized zirconia films on surface oxidized Ni wire substrate by chemical vapor infiltration (CVI) using ZrCl₄ and YCl₃ as metal sources and NiO as oxygen source were studied. The resultant films were cubic crystals of YSZ with a Y₂O₃ content of 1.0–3.7 mol%. The growth rate is larger than that obtained by conventional method of chemical vapor deposition (CVD), increased with the flow rate and decreased with diameter of NiO fiber. The growth rate above its thickness of 4 μm decreased with an increase in the oxidation temperature since the porosity of NiO wire might decrease with an increase in the oxidation temperature. Growth of YSZ films with the CVI method simultaneously involved CVD and electrochemical vapor deposition (EVD).