Thermal desorption and pyrolysis direct analysis in real time mass spectrometry of Nafion membrane

Perfluorosulfonic acid ionomer membranes have been widely used as proton conducting membranes in various electrochemical processes such as polymer electrolyte fuel cells and water electrolysis. While their thermal stability has been studied by thermogravimetry and analysis of low molecular weight products, their decomposition mechanism is little understood. In this study a newly developed methodology of thermal desorption and pyrolysis in combination with direct analysis in real time mass spectrometry is applied for Nafion membrane. An ambient ionization source and a high-resolution time-of-flight mass spectrometer enabled unambiguous assignment of gaseous products. Thermal decomposition is initiated by side chain detachment above 350°C, which leaves carbonyls on the main chain at the locations of the side chains. Perfluoroalkanes are released above 400°C by main chain scission and their further decomposition products dominate above 500 °C. DFT calculation of reaction energies and barrier heights of model compounds support proposed decomposition reactions.     

Centrifugally spun carbon fibers prepared from aqueous poly(vinylpyrrolidone) solutions as binder-free anodes in lithium-ion batteries

Aqueous solutions of poly(vinylpyrrolidone) (PVP) of various concentrations (20, 25, and 28 wt%) were successfully spun into fibers by centrifugal spinning. The pristine PVP fibers were annealed and carbonized to produce flexible carbon fibers for use as binder-free anodes in lithium-ion batteries. These flexible carbon fibers were prepared by developing a novel three-step heat treatment to reduce the residual stresses in the pristine PVP precursor fibers, and to prevent fiber degradation during carbonization. The thermogravimetric analysis data showed that the annealed fibers yielded a residual mass percentage of 36.0% while the pristine PVP fibers suffered a higher mass loss and only retained 26.5% of original mass above 450 °C (under nitrogen). The electrochemical performance of the carbon-fiber anodes was evaluated by conducting galvanostatic charge/discharge, rate performance, and cycle voltammetry experiments. The 20, 25, and 28 wt% derived binder-free anodes delivered specific charge capacities of 205, 189, and 275 mAh g⁻¹, respectively, after the first cycle at a current density of 100 mA g⁻¹. The results obtained in this work indicate that a feasible pathway towards a large-scale production of carbon-fiber anodes from a 100% aqueous solution can be achieved via centrifugal spinning and subsequent heat treatment.     

对“垃圾衍生燃料”RDF之探析

当前,我国水泥工业在可燃废弃物应用技术方面都还处于一家一户、自制自用、效率极低的初级阶段。发达国家的替代燃料:“垃圾衍生燃料”RDF、“固体回收燃料”SRF、“次煤”Subcoal和“纸塑垃圾衍生燃料”RPF制成的原材料都是可燃废弃物,只是处理工艺技术不同或者由垃圾中分拣出的可燃废弃物不同,制成颗粒状衍生燃料的品质不同,这些都可以替代部分甚或替代全部化石燃料在水泥窑炉中应用。我国大力发展“替代燃料”产业,有助于水泥工业消纳更多的“可燃废弃物”,为改善环境尤其是城镇环境和面貌,为我国的节能减排和绿色高质量发展发挥更大的作用。     

生物质基喷气燃料的生产及应用进展

生物质基喷气燃料是指全部或大部分来源于生物资源的喷气燃料，符合清洁低碳、安全高效的现代能源体系的要求。以生物质基喷气燃料替代传统石油基喷气燃料有助于我国早日实现“碳达峰、碳中和”的远大目标。在阐述生物质基喷气燃料生产工艺的发展历程及生物质基喷气燃料应用现状的基础上，提出高密度的生物质基喷气燃料是未来喷气燃料的发展方向，具有多环结构的生物质是合成高密度生物质基喷气燃料组分的优质原料；同时，总结了高密度生物质基喷气燃料组分生产工艺的研究进展，展望了生物质基喷气燃料未来的发展及挑战。     

Non-Platinum Group Metal Electrocatalysts toward Efficient Hydrogen Oxidation Reaction

Developing non-platinum group metal (non-PGM) electrocatalysts for the hydrogen oxidation reaction (HOR) represents the efforts towards the more economical use of hydrogen fuel cells and hydrogen energy, which has attracted tremendous attention recently. However, non-PGM electrocatalysts for the HOR are still in their early development stages as compared with the significant advances in those for the oxygen reduction reaction and hydrogen evolution reaction. Herein, this paper summarizes the recent progresses and highlights the key challenges for the rational design of non-PGM electrocatalysts, aiming to promote the development of non-PGM HOR electrocatalysts. Fundamental understandings of the HOR mechanism are firstly reviewed, where theoretical interpretations on the low HOR kinetics in alkaline media, including the hydrogen binding energy theory, the bifunctional mechanism, and the water molecule reorganization, are particularly discussed. Subsequently, progresses of typical non-PGM HOR electrocatalysts in acid and alkaline media are summarized separately. For the HOR under alkaline conditions, the superiorities and challenges of Ni-based catalysts are discussed with a particular focus as they are the most promising non-PGM electrocatalysts. Finally, this paper highlights the challenges and provide perspectives on the future development directions of non-PGM HOR electrocatalysts.     

Moderate temperature sintering of BaZr0.8Y0.2O3-δ protonic ceramics by A novel cold sintering pretreatment

The state-of-the-art protonic ceramic conductor BaZr_0.8Y_0.2O_3-δ (BZY20) requires an extremely high sintering temperature (≥1700 °C) to achieve the desired relative density and microstructure necessary to function as a proton conducting electrolyte. In this work, we developed a cold sintering pretreatment assisted moderate-temperature sintering method for the fabrication of high-quality pure BZY20 pellets. BZY20 pellets with high relative density of ~94% were fabricated with a final sintering temperature of 1500 °C (200 °C lower than the traditional sintering temperature). A comparison with BZY20 control samples indicated that the proper amount of BaCO₃ introduced on the BZY20 particle surface and the high green density achieved by cold sintering pretreatment were the main drivers for lowering the sintering temperature. The electrical conductivity measurement by electrochemical impedance spectroscopy showed that the as-prepared BZY20 pellets have a proton conductivity comparable to the state-of-the-art values. The cold sintering pretreatment outlined in this work has the potential to lower the sintering temperatures for similar types of protonic ceramic materials under consideration for a wide range of energy conversion and storage applications.     

Sputtered Fe1·5CoNi0.5 coating: An improved protective coating for SOFC interconnect applications

In an attempt to optimize the properties of FeCoNi coating for planar solid oxide fuel cell (SOFC) interconnect application, the coating composition is modified by increasing the ratio of Fe/Ni. An Fe_1·5CoNi_0.5 (Fe:Co:Ni = 1.5:1:0.5, atomic ratio) metallic coating is fabricated on SUS 430 stainless steel by magnetron sputtering, followed by oxidation in air at 800°C. The Fe_1·5CoNi_0.5 coating is thermally converted to (Fe,Co,Ni)₃O₄ and (Fe,Co,Mn,Ni)₃O₄ without (Ni,Co)O particles. After oxidation for 1680 h, no further migration of Cr is detected in the thermally converted coating region. A low oxidation rate of 5.9 × 10^?14 g² cm^?4 s^?1 and area specific resistance of 12.64 mΩ·cm² is obtained for Fe_1·5CoNi_0.5 coated steels.     

Ir-Pt/C composite with high metal loading as a high-performance anti-reversal anode catalyst for proton exchange membrane fuel cells

Voltage reversal induced by hydrogen starvation can severely corrode the anode catalyst support and deteriorate the performance of proton exchange membrane fuel cells. A material-based strategy is the inclusion of an oxygen evolution reaction catalyst (e.g., IrO₂) in the anode to promote water electrolysis over harmful carbon corrosion. In this work, an Ir-Pt/C composite catalyst with high metal loading is prepared. The membrane-electrode-assembly (MEA) with 80 wt% Ir-Pt(1:2)/C shows a first reversal time (FRT) of up to 20 hours, which is about ten times that of MEA with 50 wt% Ir-Pt(1:2)/C does. Furthermore, the MEA with 80 wt% Ir-Pt(1:2)/C exhibits a minimum cell voltage loss of 6 mV@1 A/cm² when the FRT is terminated in 2 hours, in which the MEA with 50 wt% Ir-Pt(1:2)/C exhibits a voltage loss of 105 mV@1 A/cm². Further physicochemical and electrochemical characterizations demonstrate that the destruction of anode catalyst layer caused by the voltage reversal process is alleviated by the use of the composite catalyst with high metal loading. Hence, our results reveal that the combination of OER catalyst on the Pt/C with high metal loading is a promising approach to alleviate the degradation of anode catalyst layer during the voltage reversal process for PEMFCs.     

稳产国Ⅵ柴油并兼产喷气燃料技术方案的工业应用

介绍了浙江石油化工有限公司新建的3 Mt/a柴油加氢精制装置，其配套使用中国石化石油化工科学研究院有限公司开发的催化剂级配技术，并实施了可根据原料供应及市场产品需求情况灵活调整切换的2种生产技术方案。1 a的安稳生产运行结果表明:该装置以直馏柴油为主原料，通过分馏塔的馏分切割及其侧线抽出，实现了稳产国Ⅵ柴油并兼产喷气燃料技术方案的工业化应用；在实施以兼产喷气燃料为主的生产技术方案时，通过调整常一线柴油的掺炼量，不仅可以生产含硫量小于10.0 μg/g的精制柴油产品，同时兼产所得到的喷气燃料产品含硫量小于0.5 μg/g，赛波特颜色号值大于30；在实施主产精制柴油组分方案时，通过掺炼质量分数为20%~40%的催化柴油，并使所提炼得到的精制柴油组分含硫量小于6.0 μg/g的前提下，这些精制柴油组分产品既可直接作为满足国Ⅵ柴油产品出厂待售，也可作为柴油调和组分储存待用于产品的进一步优化。     

Manufacturing catalyst-coated membranes by ultrasonic spray deposition for PEMFC: Identification of key parameters and their impact on PEMFC performance

This study deals with the manufacturing of catalyst-coated membranes (CCMs) for newcomers in the field of coating. Although there are many studies on electrode ink composition for improving the performance of proton-exchange membrane fuel cells (PEMFCs), there are few papers dealing with electrode coating itself. Usually, it is a know-how that often remains secret and constitutes the added value of scientific teams or the business of industrialists. In this paper, we identify and clarify the role of key parameters to improve coating quality and also to correlate coating quality with fuel cell performance via polarization curves and electrochemical active surface area measurements. We found that the coating configurations can affect the performance of lab-made CCMs in PEMFCs. After the repeatability of the performance obtained by our coating method has been proved, we show that: (i) edge effects, due to mask shadowing - cannot be neglected when the active surface area is low, (ii) a heterogeneous thickness electrode produces performance lower than a homogeneous thickness electrode, and (iii) the origin and storage of platinum on carbon powders are a very important source of variability in the obtained results.