Pd-Ag膜电解浓缩氚的动力学模型及理论计算

建立了模拟Pd-Ag合金膜电解浓缩氚的过程和诸多电解参数的动力学模型。采用求解数学扩散方程的方法得到理论值,并与文献报道的实验数据进行比较。计算结果表明：氚在Pd-Ag膜上的吸附、解吸、浓缩等行为受到诸多条件的制约。在保证密封性能的前提下,对Pd-Ag膜电解槽体的要求是至少应包括有含氚水路循环、阳极气体消除和阴极扩散后氚再生3个组成部分,采取相匹配的级联技术可以提高分离效果;对电解参数的要求是采取尽可能高的电解液温度和稳定的OH^-浓度,合适的电流密度,合理的膜厚度、表面特征和Pd黑结合紧密。     

含CO_2的蒸汽凝结换热实验研究

钙基吸收剂锻烧碳酸化循环法能够有效地控制CO2的排放,其中CaCO3的煅烧过程中加入适量水蒸气能够降低煅烧温度,节约成本,对尾气进行冷凝处理能够得到相对浓度较高的CO2,研究了含CO2的蒸汽在水平圆管上的凝结换热特性,从气相边界层与液膜变化的角度对实验结果做出了解释,并总结了凝结换热经验公式。     

Electrochemical performance of mixed ionic–electronic conducting oxides as anodes for solid oxide fuel cell

Mixed ionic–electronic conducting (MIEC) oxides, SrFeCo_0.5O_x, SrCo_0.8Fe_0.2O_3−δ and La_0.6Sr_0.4Fe_0.8Co_0.2O_3−δ have been synthesized and prepared on yttria-stabilized zirconia as anodes for solid oxide fuel cells. Power output measurements show that the anodes composed of such kinds of oxides exhibit modest electrochemical activities to both H₂ and CH₄ fuels, giving maximum power densities of around 0.1 W/cm² at 950°C. Polarization and AC impedance measurements found that large activation overpotentials and ohmic resistance drops were the main causes for the relative inferior performance to the Ni-YSZ anode. While interlayered with an Ni-YSZ anode, a significant improvement in the electrochemical performance was observed. In particular, for the SrFeCo_0.5O_x oxide interlayered Ni-YSZ anode, the maximum power output reaches 0.25 W/cm² on CH₄, exceeding those of both SrFeCo_0.5O_x and the Ni-YSZ, as anodes alone. A synergetic effect of SrFeCo_0.5O_x and the Ni-YSZ has been observed. Future work is needed to examine the long-term stability of MIEC oxide electrodes under a very reducing environment.     

可调谐半导体激光吸收光谱法监测二氧化碳的通量

含碳温室气体浓度增加所加剧的温室效应是气候变化的重要原因,大面积范围内二氧化碳气体通量的测量对于评价各类陆地生态系统对大气中主要温室气体浓度的贡献具有重要的意义。可调谐半导体激光吸收(TDLAS)光谱技术具有高分辨率、高灵敏度以及快速响应等特点,是痕量气体高灵敏快速监测的新方法。文章以可调谐分布反馈半导体激光器作为光源,通过波长调制方法对1.573μm附近二氧化碳气体某一吸收线的二次谐波信号测量,结合激光分束技术,实现对不同高度层面700多米光程范围内二氧化碳气体浓度的快速在线检测。结合大口径闪烁仪测量出来的莫宁-奥布霍夫长度和特征速度,通过公式计算得到一天内二氧化碳气体的通量在-1.5～2.5mg·(m2·s)-1范围内的波动,突破了目前对近地面痕量气体通量的监测只能提供局地结果的状况,使大面积范围内痕量气体通量的测量成为可能。     

On the reversibility of anode supported proton conducting solid oxide cells

Reversible proton conducting solid oxide cells (SOCs) off a highly efficient route to matching supply from intermittent, renewable resources, with power demand by consumers. The cells would store excess electrical energy as chemical fuel during times of peak production, and operate in reverse during times of peak demand. In this study we examine the operation of anode supported proton conducting SOCs in electrolysis mode. The required overpotential for a given current density decreases with increasing humidity at the anode and increasing temperature. All of the V-I curves show distinct curvature. The electrode polarization resistance increases and electrolyte ohmic resistance decreases with increasing current density. This is accompanied by a deviation below the theoretical rate of hydrogen production. We interpret these changes as resulting from deviation away from pure proton conduction in the cell with increasing polarization.     

Co-electrolysis of CO2 and H2O in solid oxide cells: Performance and durability

This study examines the initial performance and durability of a solid oxide cell applied for co-electrolysis of CO₂ and H₂O. Such a cell, when powered by renewable/nuclear energy, could be used to recycle CO₂ into sustainable hydrocarbon fuels. Polarization curves and electrochemical impedance spectroscopy were employed to characterize the initial performance and to break down the cell resistance into the resistance for the specific processes occurring during operation. Transformation of the impedance data to the distribution of relaxation times (DRT) and comparison of measurements taken under systematically varied test conditions enabled clear visual identification of five electrode processes that contribute to the cell resistance. The processes could be assigned to each electrode and to gas concentration effects by examining their dependence on gas composition changes and temperature.This study also introduces the use of the DRT to study cell degradation without relying on a model. The durability was tested at consecutively higher current densities (and corresponding overpotentials). By analyzing the impedance spectra before and after each segment, it was found that at low current density operation (− 0.25 A/cm² segment) degradation at the Ni/YSZ electrode was dominant, whereas at higher current densities (− 0.5 A/cm² and − 1.0 A/cm²), the Ni/YSZ electrode continued to degrade but the serial resistance and degradation at the LSM/YSZ electrode began to also play a major role in the total loss in cell performance. This suggests different degradation mechanisms for high and low current density operation.     

Effect of cation doping on ionic and electronic properties for lanthanum silicate-based solid electrolytes

Electronic as well as ionic conducting properties for oxyapatite-type solid electrolytes based on lanthanum silicate, La_9.333 + xSi₆O_26 + 1.5x (LSO) were investigated in the oxygen-excess region (x > ca. 0.3). We have found that the oxygen excess-type LSO (OE-LSO), namely La₁₀Si₆O₂₇ on weighted basis, exhibited high conductivity, and substitution of the Si-site of LSO with some dopants (Mⁿ⁺) had a positive effect toward the conducting property. Furthermore, it was also found that addition of a very small amount of iron ions into the M-doped OE-LSO, La₁₀(Si_6-yMⁿ⁺_y)O_27-(2-0.5n)y, improved its conductivity. On the other hand, replacement of the La-site with various ions for La₁₀(Si_6-yMⁿ⁺_y)O_27-(2-0.5n)y did little to improve conductivity. The electronic transport numbers for Al-doped OE-LSO with Fe-addition, (1-α){La₁₀(Si_5.8Al_0.2)O_26.9}-α(FeO_γ), evaluated with the Hebb-Wagner polarization method were very low: i.e., 1.1 × 10^− 3 and 2.9 × 10^− 3 under P(O₂) = 1.1 × 10⁴ Pa at 1073 K for α = 0.00 and 0.005, respectively. Conductivity for each sample was unchanged under humidified atmosphere at 1073 K sustained for over 50 h, revealing that both compositions were chemically stable. It was concluded that 0.995{La₁₀(Si_5.8Al_0.2)O_26.9}-0.005(FeO_γ) is suitable for the fuel cell electrolytes because of its high and almost pure ionic conductivity, and its good chemical stability under humidified as well as reducing conditions.     

Near infrared spectroscopy of carbon dioxide I. OCO line positions

High-resolution near-infrared (4000-9000 cm⁻¹) spectra of carbon dioxide have been recorded using the McMath-Pierce Fourier transform spectrometer at the Kitt Peak National Solar Observatory. Some 2500 observed positions have been used to determine spectroscopic constants for 53 different vibrational states of the ¹⁶O¹²C¹⁶O isotopologue, including eight vibrational states for which laboratory spectra have not previously been reported. Calibration by simultaneous use of CO near 4200 cm⁻¹ and C₂H₂ near 6500 cm⁻¹ provides absolute line position accuracies of 6.0 × 10⁻⁵ cm⁻¹ (RMS) for strong, isolated transitions throughout the observed range. Fits with RMS errors <3.8 × 10⁻⁵ cm⁻¹ have been obtained for the 20013 ← 00001, 20012 ← 00001, and 20011 ← 00001 bands, RMS errors <6 × 10⁻⁵ cm⁻¹ have been obtained for the 30014 ← 00001, 30013 ← 00001, 30012 ← 00001, and 00031 ← 00001 bands, and RMS errors <5 × 10⁻⁴ cm⁻¹ for even the weakest fitted bands. This work reduces CO₂ near-infrared line position uncertainties by a factor of 10 or more compared to the 2000 HITRAN line list, which has not been modified since the comprehensive work of Rothman et al. [J. Quant. Spectrosc. Rad. Transfer 48 (1992) 537]. The new line list satisfies the line position accuracies required for the next generation of CO₂ remote sensing instruments, improves the capability of solar-viewing spectrometers to retrieve precise column CO₂ measurements, and provides a secondary frequency standard in the near-infrared.     

Characterization of solid oxide fuel cells based on solid electrolytes or mixed ionic electronic conductors

The relation between cell voltage (V_cell), applied chemical potential difference (Δμ(O₂)) and cell current (I_t) for solid oxide fuel cells (SOFC) based on mixed ionic electronic conductors is derived by considering also the effect of electrode impedance. Four-probe measurements, combined with current interruption analysis, are considered to yield the relation between ionic current (I_i) and overpotential (η). The theoretical relations are used to analyze experiments on fuel cells with Ce_0.8Sm_0.2O_1.9 and Ce_0.8Gd_0.2O_1.9 electrolytes with La_0.8Sr_0.16CoO₃ or Pt as the cathode and Ni/Ce_0.9Ca_0.1O_1.9−xor Pt as the anode. The electrode overpotentials of these cells, determined by current interruption measurements, are discussed assuming different models including impeded mass transport in the gas phase for molecular and monoatomic oxygen and Butler-Volmer type charge transfer overpotential.     

Tuning properties of NC3H quantum dot by adsorption of ammonia and carbon dioxide

Transport properties of NC₃H quantum dot by adsorption of ammonia and carbon dioxide are investigated with an ab initio method combined with a non-equilibrium Green function method. The effects of different configurations of ammonia, size of NC₃H surface and position where ammonia and carbon dioxide had been adsorbed onto NC₃H quantum dot on transport properties are revealed. In comparison with NC₃H quantum dot device, results show that the adsorption of ammonia molecule on NC₃H quantum dot in one configuration enhances the conductance of device, while adsorption in another configuration reduces the conductance. The size of NC₃H significantly altered the transport properties in both NC₃H–NH₃ and NC₃H–CO₂ system. The position of adsorption of ammonia displays obvious change on transport properties while the effects of position of carbon dioxide on transport properties are negligible.     

固态二氧化碳电子结构及性能的理论研究

采用基于赝势平面波理论的第一性原理计算方法,研究了9种结构的固态二氧化碳的结构和性质.经过结构的几何优化,得到α石英稳定结构晶格常数与他人的计算值基本一致.通过对平衡态能量的分析,我们得出β方石英(cristobalite)结构是能量最低的结构.这与文献的研究结果一致.对弹性性质的计算结果表明,除了超石英(stishovite)和立方黄铁矿(cubic-pyrite)结构之外,其他的结构都是弹性稳定的.利用基于Mulliken轨道重叠布居数的共价固体本征硬度计算方法,预测了各个结构的本征硬度值.结果表明, 关键词： 第一性原理计算 固态二氧化碳 电子结构 硬度     

利用溶液理论计算饱和甲烷中二氧化碳溶解度

求取二氧化碳在饱和液态甲烷中的溶解度,对于在较高温度下实现液化天然气至关重要。文中在理想溶液基础上,采用正规溶液关系式和改进的Scatchard-H ildebrand关系式进行二氧化碳的溶解度计算,并且在临界点附近采用经验公式对其进行修正。将上述计算结果与Davis实验数据进行比较后表明,改进的正规溶液理论计算方法在低于140K温区时可推荐用于此项溶解度计算,经验公式可用于接近临界温度区域的溶解度计算。     

High temperature oxidation behavior of interconnect coated with LSCF and LSM for solid oxide fuel cell by screen printing

The current study examined the effect of La_0.6Sr_0.4Co_0.2Fe_0.8O₃ (LSCF) and La_0.7Sr_0.3MnO₃ (LSM) coatings on the electrical properties and oxidation resistance of Crofer22 APU at 800 °C hot air. LSCF and LSM were coated on Crofer22 APU by screen printing and sintered over temperatures ranging from 1000 to 1100 °C in N₂. The coated alloy was first checked for compositions, morphology and interface conditions and then treated in a simulated oxidizing environment at 800 °C for 200 h. After measuring the long-term electrical resistance, the area specific resistance (ASR) at 800 °C for the alloy coated with LSCF was less than its counterpart coated with LSM. This work used LSCF coating as a metallic interconnect to reduce working temperature for the solid oxide fuel cell.     

Variable-temperature FT-IR studies on the thermodynamics of carbon dioxide adsorption on a faujasite-type H-Y zeolite

Adsorption of carbon dioxide on a faujasite-type H-Y zeolite (Si:Al = 2.6:1) was studied by variable-temperature (200-290 K range) infrared spectroscopy. Adsorbed CO₂ molecules interact with the Brønsted acid Si(OH)Al groups located inside the zeolite supercage, bringing about a characteristic bathochromic shift of the O-H stretching mode from 3645 cm⁻¹ (free OH group) to 3540 cm⁻¹ (hydrogen-bonded CO₂ adsorption complex). Simultaneously, the asymmetric (ν₃) mode of adsorbed CO₂ is observed at 2353 cm⁻¹. From the observed variation of the integrated intensity of the 3645 and 2353 cm⁻¹ IR absorption bands upon changing temperature, corresponding values of standard adsorption enthalpy and entropy were found to be ΔH° = −28.5(±1) kJ mol⁻¹ and ΔS° = −129(±10) J mol⁻¹ K⁻¹. Comparison with the reported values of ΔH° for CO₂ adsorption on other zeolites is briefly discussed.     

An experimental study on the effect of mesoporous silica addition on ion conductivity of poly(ethylene oxide) electrolytes

Solid polymer electrolyte (SPE) composites, which are composed of poly(ethylene oxide) (PEO), mesoporous silica (SBA-15), and lithium salt were prepared in order to investigate the influence of SBA-15 content on the ionic conductivity of the composites. The ionic conductivity of the SPE composites was monitored by frequency response analyzer (FRA), and the crystallinity of the SPE composites was evaluated by using XRD. As a result, the addition of SBA-15 to the polymer mixture inhibited the growth of PEO crystalline domain, due to the mesoporous structure of the SBA-15. Also, the PEO₁₆LiClO₄/SBA-15 composite electrolytes show an increased ion conductivity as a function of SBA-15 content up to 15 wt.%. These ion conductivity characteristics are dependent on crystallinity with SBA-15 content.     

Environmentally benign nanomixing by sonication in high-pressure carbon dioxide

Due to the increased use of nanocomposites, mixing at nanoscale has become important. Current mixing techniques can be classified into: (a) dry mixing (mechanical mixing), (b) wet mixing, and (c) simultaneous production of mixed nanoparticles (when possible). Dry mixing is in general not effective in achieving desired mixing at nanoscale, whereas wet mixing suffers from different disadvantages like nanomaterial of interest should be insoluble, has to wet the liquid, and involves additional steps of filtration and drying. This paper examines the use of pressurized carbon dioxide having high density and low viscosity to replace the liquids (e.g., n-hexane, toluene). Ultrasound is applied to the suspension of nanopowders in gaseous and supercritical carbon dioxide where high impact collisions during sonication help mixing and the final mixture is obtained by simple depressurization. The method is tested for binary mixture of alumina/silica, silica/titania, MWNT (multiwalled carbon nanotubes)/silica, and MWNT/titania. The effects of sonication intensity and pressure on the degree of mixing are studied. Comparative study is also done with liquid n-hexane as a mixing media. Quantitative characterization (e.g., mean composition standard deviation, intensity of segregation) of mixing of alumina/silica and silica/titania is done with energy-dispersive X-ray spectroscopy, and that of MWNT/silica and MWNT/titania is done using field-emission scanning electron microscopy and day-light illumination spectrophotometry. Results show that mixing in carbon dioxide at higher ultrasound amplitudes is as good as in liquid n-hexane, and the final mixed product does not contain any residual media as in the case of liquid n-hexane.     

Direct ammonia proton-conducting solid oxide fuel cells prepared by a modified suspension spray

A dense (BCSO) membrane was fabricated by a modified suspension spraying on porous NiO–BCSO anode support. In the process, the suspension was directly prepared by ball-milling the BaCO₃, CeO₂, and Sm₂O₃ powders in ethanol. A dense and uniform electrolyte layer in the thickness of 10 μm was successfully prepared on porous anode support by suspension spray process after co-sintering at 1,400 °C for 5 h. With (NSMO) cathode, a single cell was assembled and tested with hydrogen and ammonia as fuels, respectively. The hydrogen-fueled cell exhibits 1.01 V for open circuit voltage (OCV) and 560 mW/cm² for peak power density at 700 °C. In comparison, the cell in ammonia displays a similar performance (1.02 V for OCV and 530 mW/cm² for output), which indicates the liquid ammonia is a promising substitute for hydrogen. Moreover, the fuel cell displays good interface contacts. To sum up, ammonia-fueled solid oxide fuel cells prepared by this simple suspension spray is an alternative way to promote the commercialization.     

Preparation and ablation properties of ZrC-SiC coating for carbon/carbon composites by solid phase infiltration

A novel ZrC-SiC coating was prepared on carbon/carbon (C/C) composites surface by solid phase infiltration and the ablation properties of the ZrC-SiC coated C/C composites under oxyacetylene flame were studied. The results show that the coating prepared on the condition of optimum process parameters exhibits dense surface and outstanding anti-ablation ability. After ablation for 20 s, the mass ablation rates of the coated C/C composites can be lowered to 2.36 × 10⁻³ g/s, 37.1% reduction compared with uncoated C/C composites. The oxide layer composed of ZrO₂ and SiO₂ acts as oxygen diffusion barrier and the evaporation of ZrO₂ and SiO₂ absorbs a great amount of heat from the flame and reduces the erosive attack on the coating.     

A tubular segmented-in-series solid oxide fuel cell with metallic interconnect films: A performance study through mathematical simulations

In a segmented-in-series solid oxide fuel cell (SIS-SOFC), an interconnect (IC) provides electrical contact and sealing between the anode of one cell and the cathode of the next. A metallic silver-glass composite (SGC) is considered a promising alternative to ceramic IC materials in SIS-SOFCs. In this work, a simulation study is performed on a tubular SIS-SOFC to assess the effectiveness of the SGC-IC design and to predict the SOFC performance characteristics for various IC geometries and conductivities. The developed model provides detailed information on cell behavior, such as the internal resistance, the potential/current distribution, and the local gas species concentration. The results demonstrate that the SGC material greatly reduces a potential drop across the IC film. Thus, it provides the following substantial advantages over conventional ceramic IC materials: (i) increased power density and (ii) a larger degree of flexibility in the cell design. Moreover, the validation test, i.e., comparison of the simulated results with the experimental data, indicates that the model could serve as a valuable tool for design optimization to achieve the required SOFC performance.