电致变色氧化钨薄膜的干法锂化研究

采用电子束加热蒸发金属Ｌｉ对ＷＯ３电致变色薄膜进行干法锂化，利用Ｘ光电子能谱和电化学方法分析不同锂化程度ＷＯ３薄膜的化学组分和电致变色性能。实验表明，当锂化ＷＯ３薄膜中Ｌｉ原子与Ｗ原子的数目比在０．１５左右时有良好的可逆性和着色效率。利用该方法制备了性能良好的单片式导Ｌｉ＋全固态电致变色薄膜器件Ｇｌａｓｓ／ＩＴＯ／ＷＯ３·Ｌｉ／ＬｉＦ·ＡｌＦ３／Ｖ２Ｏ５／Ａｌ。     

射频溅射沉积TaOx薄膜离子导体性能

利用射频反应溅射沉积方法在不同氧含量下以ＷＯ３／ＩＴＯ／Ｇｌａｓｓ为基体，制备了一系列厚度大于２００ｎｍ的ＴａＯｘ薄膜，并用Ａｒｎｏｌｄｕｓｓｅｎ方法检测离子导电性能。结果表明，当溅射功率为１５０Ｗ、氧含量１０～８０％条件下制备的ＴａＯｘ薄膜均为离子导体。其中氧含量２０—４０％时离子导电性能最佳。用ＴａＯｘ薄膜作为离子导体制备的Ａｌ／ＮｉＯｘ／ＴａＯｘ／ＷＯｘ／ＩＴＯ／Ｇｌａｓｓ电致变色器件，其着色态在可见光谱范围（０．３８—０．７８μｍ）的平均反射比为１１．２％，漂白态时对应的平均反射比可达８３．２％。本文还讨论了ＴａＯｘ离子导体的离子导电机理。     

载体对镍基氨分解催化剂催化性能的影响

用不同的载体（ＭｇＯ、α－Ａｌ２Ｏ３、γ－Ａｌ２Ｏ３和ＭｇＡｌ２Ｏ４）制备了４种镍基催化剂并对它们进行了氨分解活性评价。采用ＴＰＲ技术研究了这些催化剂的还原行为及载体表面和ＮｉＯ组分的相互作用,并用ＸＲＤ对催化剂的固相结构进行了表征。     

NiOxHy薄膜电致变色性能的研究

利用直流磁控溅射法，在Ｏ２＋Ｈ２的气氛下制备了ＮｉＯｘＨｙ薄膜，研究了不同氢气含量对薄膜的初始沉积态、漂白态和着色态透光性能的影响，含氢量为８０％时，薄膜的初始沉积态的平均可见光透射比最高。含氢量为６０％时，薄膜的电致变色能力最佳。用获得的ＮｉＯｘＨｙ薄膜制备的反射型全固态电致变色器件的控光范围可达７７％。对ＮｉＯｘＨｙ薄膜三种状态的红外吸收光谱分析表明，ＮｉＯｘＨｙ薄膜的变色机理可用：Ｎｉ（ＯＨ）２（漂白态）＝ＮｉＯＯＨ（着色态）＋Ｈ＋＋ｅ－表示。     

有机液体氢化物贮氢新技术研究：Ⅰ.Ni／Al2O3催化剂甲苯气相加氢…

应用工业三叶草型Ｎｉ／Ａｌ２Ｏ３催化剂对甲苯的贮氢反应及其动力学模型进行了研究，结果表明：工业Ｎｉ／Ａｌ２Ｏ３催化剂是性能优良的甲苯贮氢催化剂；在压力０．１２ＭＰａ（绝），温度９０－１５０℃，甲苯转化率０－１００％的实验条件下，该反应呈零级反应，其反应活化能为４９．３ｋＪ／ｍｏｌ。     

GaAs太阳电池帽层腐蚀研究--GaAs/AlGaAs薄膜体系的选择性腐蚀

由ｐ＋－ＧａＡｓ帽层和ｐ－ＡｌｘＧａ１－ｘＡｓ（ｘ＝０·８—０．９）窗口层构成的异质薄膜体系是ＧａＡｓ太阳电池器件中的常规结构。对该异质结构的只腐蚀ＧａＡｓ而不腐蚀ＡｌＧａＡｓ的选择性腐蚀工艺是ＧａＡｓ太阳电池制备过程中的一道关键工序。针对传统腐蚀工艺中出现的腐蚀后露出的ＡｌＧａＡｓ表面呈现彩色的问题,从改进腐蚀液配方角度,围绕通常采用的氨水－双氧水（ＮＨ４ＯＨ－Ｈ２Ｏ２）腐蚀液体系,对该问题作了深入细致的专门研究,并与柠檬酸－双氧水（Ｃ６Ｈ８Ｏ７－Ｈ２Ｏ２）和柠檬酸－柠檬酸钾－双氧水（Ｃ６Ｈ８Ｏ７－Ｋ３Ｃ６Ｈ５Ｏ７－Ｈ２Ｏ２）腐蚀液体系作对比,最终得到了较满意的氨水－双氧水－磷酸（ＮＨ４ＯＨ－Ｈ２Ｏ２－Ｈ３ＰＯ４）新腐蚀液体系。这种腐蚀液体系不仅可在较宽的溶液浓度范围内实现对高Ａｌ组分ＧａＡｓ／ＡｌＧａＡｓ异质结构的选择性腐蚀,而且也不会对露出的ＡｌＧａＡｓ外观产生明显影响     

粉煤流化床燃烧中N2O的生成特性

粉煤流化床（ＰＣ－ＦＢ）是一项燃烧效率高,同时实现炉内脱硫,低ＮＯｘ和Ｎ２Ｏ排放的新型高效、清洁煤燃烧技术,在一座０．３ＭＷ的试验台上,研究了其Ｎ２Ｏ生成与分布特性,包括床层温度Ｔｂ、流化速度Ｕｏ、二次风率Ｒ２,ＰＣ－ＦＢ流化床燃烧区（ＦＢＣＺ）出口氧浓度Ｏ２、钙硫化（Ｃａ／Ｓ）对ＦＢＣＺ出口Ｎ２Ｏ浓度的影响;以及各层二次风份额（Ｒ２ｉ％）及悬浮空间燃烧区（ＦＣＺ）的温度分布与炉内Ｎ２Ｏ浓度分布的     

降解五氯酚(PCP)厌氧生物反应器起动过程的特性研究

在实验室规模的两个厌氧反应器中,分别添加ＰＣＰ啤酒厂糖化废水与柠檬酸生产废水作为进水,以未经驯化的厌氧污泥作为接种物,采用ＰＣＰ负荷,ＣＯＤ负荷递增方式进行反应器启动。结果证实反应器的运行性能随污泥颗粒化进程而得到改善,其稳态运行性状为;ＨＲＴ２４ｈ,ＰＣＰ负荷９７．３－１０５．６ｍｇ／Ｌ．ｄ,ＣＯＤ负荷４．３－６．２ｇ／Ｌ．ｄ,ＰＣＲ去除率１００％,ＣＯＤ去除率９３．１－９５．７５,容积产沼气率     

磁控溅射电致变色非晶态氧化钨薄膜

利用平面磁控反应溅射在具有透明导电膜的玻璃基片上沉积氧化钨膜层。Ｘ射线衍射分析结果表明，基片在室温状态下得到的膜呈非晶态。以０．２Ｎ浓度的ＨＣｌ为电解液，用电化学方法研究了Ｈ＋注入及抽出后氧化钨膜光学性能的变化及这种变化与膜的制备参数之间的关系。获得了沉积氧化钨膜近于最佳的工艺条件。在纯氧气氛下，溅射功率密度１．２Ｗ／ｃｍ２，溅射气体压强１．３Ｐａ时，制备的非晶态氧化钨膜，在５０次电化学循环后，漂白态与着色态的可见光透射率之差约为０．５７，其电化学循环的变色寿命也长。光电子能谱（ＸＰＳ）分析表明，Ｈ＋注入后着色态膜内出现了Ｗ５＋、Ｗ４＋。对电致变色机理也作了讨论。     

粉煤流化床(PC-FB)燃烧的NO生成与排放控制特征

粉煤流化床（ＰＣ－ＦＢ）是一项燃烧效率高,同时实现炉内脱硫、低ＮＯｘ和Ｎ２Ｏ排放的新型高效、清洁煤燃烧技术。在１座０．３ＭＷ的试验台上研究了其ＮＯ生成与排放控制特性。主要研究内容包括：各层二次风份额（Ｒ２ｉ％）及悬浮空间燃烧区（ＦＣＺ）的温度分布与炉内ＮＯ浓度分布的关系;床层温度Ｔｂ、流化速度Ｕｏ、二次风率Ｒ２、ＰＣ－ＦＢ流化床燃烧区（ＦＢＣＺ）出口氧浓度Ｏ’２、钙硫化（Ｃａ／ｓ）等对ＰＢＣＺ出口ＮＯ浓度ＮＯ’、ＰＣＦＢ炉膛出口ＮＯ浓度ＮＯ”的影响。图１２参１０     

电沉积法制备电致变色材料

应用电沉积法制备WO3、NiO、M0O3,WO3/M0O3等电致变色薄膜。WO3薄膜、NiO薄膜、M0O3薄膜具有较好的电致变色特性,漂白态和着色态的透射率之差平均为30％左右。WO3/M0O3掺杂薄膜漂白态和着色态的透射率之差平均为40％左右,显示掺杂有利于增强薄膜的电致变色特性。WO3 NiO互补型电致变色体系漂白态和着色态的透射率之差平均为40％左右,显示互补型电致变色材料有利于增强电致变色特性。在双注入模型的基础上,根据过渡金属配合物显色机理,提出解释电致变色机理的“配位场模型”,认为在电致变色中可能存在三种电子跃迁方式。     

互补型全固态电致变色光窗

报道了三氧化钨和氧化镍两种电致变色膜及氧亚甲基聚环氧乙烷锂离子固体电解质构成的电致变色窗的制作。测量了３５０－１０００ｎｍ小长范围内的透地谱、电流响应、光响应及其与温度的依赖关系。     

An all-solid-state electrochromic device based on NiO/WO3 complementary structure and solid hybrid polyelectrolyte

An all-solid-state electrochromic (EC) device based on NiO/WO₃ complementary structure and solid polyelectrolyte was manufactured for modulating the optical transmittance. The device consists of WO₃ film as the main electrochromic layer, single-phase hybrid polyelectrolyte as the Li⁺ ion conductor layer, and NiO film as the counter electrochromic layer. Indium tin oxide- (ITO) coated glass was used as substrate and ITO films act as the transparent conductive electrodes. The effective area of the device is 5×5 cm². The device showed an optical modulation of 55% at 550 nm and achieved a coloration efficiency of 87 cm² C⁻¹. The response time of the device is found to be about 10 s for coloring step and 20 s for bleaching step. The electrochromic mechanism in the NiO/WO₃ complementary structure with Li⁺ ion insertion and extraction was investigated by means of cyclic voltammograms (CV) and X-ray photoelectron spectroscopy (XPS).     

Performance of an electrochromic window based on polyaniline, prussian blue and tungsten oxide

In our laboratory various electrochromic windows (ECWs) have been investigated using mainly tungsten oxide (WO₃), polyaniline (PANI) and prussian blue (PB) as electrochromic materials in combination with poly(2-acrylamido-2-methyl-propane-sulphonic acid) (PAMPS) as a solid proton-conducting electrolyte. The ECWs have been characterized by AC-impedance, linear sweep voltammetry and spectroelectrochemical studies in the 290–3300 nm spectral region. The ECWs have the following general multilayered structure: Glass/ITO/EC1/IC/EC2/ITO/Glass, where ITO=indium oxide doped with tin, IC=ionic conductor, EC1 is either PANI or PANI including PB, and EC2 is WO₃. The best of these ECWs has been able to regulate up to 56% (typical 50%) of the transmission of the total solar energy in the 290–3300 nm spectral range. The combination of the two electrochromic materials PANI and PB has been shown to be mutually beneficial in such a way that the colouration of the window is enhanced by the addition of a layer of PB onto PANI, while the adhesion of PB is improved by the presence of PANI. The energy consumption of the ECW is about 0.01 Wh/m² for one complete cycle (−1.8 V/1.2 V). The switching time for 90% colouring/bleaching is typically 10–30 s. A PANI/PB//WO₃ window has been operated for about 50 days (3700 complete cycles) without substantial loss of transmission regulation, though with an increase in switching time (10 min.). Spectra from individual layers in the ECWs have been recorded by making holes in one or two of the electrochromic layers. In this way (the hole method), it has been possible to study the transmission regulation properties for each electrochromic material separately in complete solid state windows. In addition, spectra for complete windows have been simulated by adding contributions from individual electrochromic layers.     

Hydrogen production by chemical-looping reforming in a circulating fluidized bed reactor using Ni-based oxygen carriers

This work presents the experimental results obtained during auto-thermal chemical-looping reforming (CLR) in a 900 W_th circulating fluidized bed reactor under continuous operation using methane as fuel. Two oxygen carriers based on NiO and supported on γ-Al₂O₃ and α-Al₂O₃ were used during more than 50 h of operation with each oxygen carrier. During operation the effect of different operating variables, like fuel reactor temperature, H₂O/CH₄ molar ratio and solid circulation rate, on CH₄ conversion and gas product distribution was analyzed. It was found that in all operating conditions CH₄ conversion was very high (>98%) and the most important variable affecting to the gas product distribution was the solid circulation rate, that is, NiO/CH₄ molar ratio. Similar gas product distribution was obtained working with both oxygen carriers although at different NiO/CH₄ molar ratios. The oxygen carrier of NiO on α-Al₂O₃ needed lower NiO/CH₄ molar ratio to reach the same gas product composition than the oxygen carrier of NiO on γ-Al₂O₃. Working at optimal operating conditions, 2.5 moles of H₂ per mol of CH₄ could be obtained in this process.During operation the oxygen carrier particles maintained their physical and chemical properties. These results suggest that these oxygen carriers could have a high durability, being suitable oxygen carriers for a CLR system.     

锂盐对LAGP-PEO复合固体电解质及全固态LFP锂离子电池性能的影响

将Li1.5Al0.5Ge1.5(PO4)3（LAGP）与少量PEO(LiX)复合,采用溶液浇注法制备了以LAGP为主相的固体复合电解质,研究了LiClO4、LiTFSI、LiBOB 3种锂盐对固体复合电解质离子电导率、电化学稳定窗口、与锂负极界面的化学稳定性和电化学稳定性的影响以及锂盐种类对LFP固态电池循环及倍率性能的影响。研究结果表明,采用LiClO4、LiTFSI、LiBOB 3种锂盐制备的固体复合电解质分解电压均超过5 V,具有较好的电化学稳定性。LAGP-PEO(LiTSFI)固体复合电解质的离子电导率以及室温对锂界面的稳定性相对更高。LAGP-PEO (LiBOB)与锂的界面在60 ℃时相对更稳定。与之对应,采用LAGP-PEO(LiTSFI)和LAGP-PEO(LiBOB)固体复合电解质的LFP全固态电池,分别在25 ℃和60 ℃具有最高的比容量和最好的循环稳定性。     

Preparation of NiO / PC catalyst with plasma for cracking tar to produce flammable gas

To increase the use of lignite, the tar was pyrolyzed with pyrolysis coke (PC) to produce more combustible gases such as H₂, CH₄, and CO. NiO/PC catalyst with plasma was prepared, and the influence of PC and NiO/PC catalyst on flammable gas was investigated in a two-stage fixed reactor. The catalysts were characterized by SEM, BET, XPS and XRD to analyze the tar cracking mechanism. The results were: (1) PC was prepared at different heating rates, and when the heating rate reached 20 °C/min, the amount of flammable gas was 5.4 L. (2) NiO/PC catalyst was modified with plasma in three background gases withO₂ being the best, mainly because of the increase of the oxygen functional groups. (3) PC was modified and calcined with plasma, and when the power reached 40 W, it produced the most combustible gas, and the volume could grow by 94.4%.     

Solubilities of NiO and LaNiO3 in Li/Na eutectic carbonate with rare-earth oxide

For the commercial application of molten carbonate fuel cells (MCFCs) under high-pressure operation, the problem of Ni shorting should be solved that is closely related to the solubility of cathode material. In order to improve the MCFC cathode stability, effects of the addition of rare-earth metal oxides to the molten carbonates have been quantitatively investigated. Especially, La₂O₃ addition to the molten carbonate significantly decreased the solubility of NiO. Such low solubility of NiO was caused by effects of both the acid-base equilibrium of molten carbonate and the activity of Ni in solid by the formation of complex oxide. Solubilities of LaNiO₃ and Nd₂NiO₄ were also smaller than that of NiO in molten carbonate as the same reason as that of NiO in the molten carbonates with saturated La₂O₃. Based on the data of solubility, a new parameter was proposed to evaluate the solubility of metal ion in molten carbonates. This parameter concerned with the acid-base equilibrium of melts and the activity of solid for the metal oxide. A linear relationship with the measured solubility of metal oxide in molten carbonates was obtained by this parameter. It would be indicated that the parameter is useful for the prediction of metal oxide solubilities in molten carbonates.     

Durability of electrochromic glazing

Fundamental properties of all-solid-state electrochromic windows to control the solar energy have been investigated. This system comprises of multilayer represented as Glass/ITO/NiO/Inorganic Electrolyte (Ta₂O₅, etc.)/ WO₃/ITO/ Adhesive Film/ Glass. Of the various electrochromic systems examined so far, the most important features are their environmental stability and the possibility of large area applications. Our system can control the visible transmittance between 72.6% and 17.6% and has a cyclic life over 100000 cycles at 60°C. Based on the accelerated weathering tests, the stability of the system is estimated to be over five years for outdoor applications. For the problem of scaling up, some technical aspect is given and the prototype window of size 40×60 cm is exemplified. The present system could be more suitable for architectural and automobile applications in the near future by developing production technology.     

Cross-sectional high-resolution transmission electron microscopy of the microstructure of electrochromic nickel oxide

Electrochromic nickel oxide films on indium tin oxide (ITO) were investigated by cross-sectional high-resolution transmission electron microscopy and energy dispersive X-ray analysis. Microstructural features and the differences between high and poor-quality samples were studied and compared. The dominant phase of the NiO film has cubic structure, but selected area electron diffraction patterns revealed many extra diffraction spots for the high-performance samples which may result from additional hydrated nickel oxide phases. The NiO grains do not show clear shapes in the cross-sectional plane nor are there signs of a preferred orientation. The mean grain size is larger and there are more defects and superlattices in samples with good electrochromic properties. There was a clear correlation between grain size distribution and performance. The high-quality samples had a mean grain size of about 6.5 nm, whereas the poor-quality samples exhibited significantly smaller mean grain sizes of 5.0 and 3.8 nm.