Oxidative conversion of CH4 on Ni and Ag electrode-catalysts in molten carbonate fuel cell reactor

A fuel cell system using molten carbonates of potassium and lithium as electrolyte was applied to the oxidative conversion of methane over Ni and Ag electrodes. A possibility of cogeneration of valuable chemicals, like C₂-hydrocarbons, and electricity in such a system was demonstrated. With CO ₃ ^2– ions (oxygen) transported electrochemically, the rate of formation of C₂-hydrocarbons and selectivity for them on the Ag electrode were found to be greater than those with oxygen premixed to the gase phase.     

A study on the chemical stability and electrode performance of modified NiO cathodes for molten carbonate fuel cells

The chemical stabilities of modified NiO cathodes doped with 1.5 mol% CoO and 1.5 mol% LiCoO₂ fabricated by a conventional tape casting method were evaluated through the real MCFC single cell operation. The heat-treated samples before oxidation had proper porosities and microstructures for a MCFC cathode. At 150 mA cm⁻² in current density, the MCFC single cell using a CoO-doped NiO cathode showed stable cell voltages in the range of 0.833-0.843 V for 1000 h. In contrast, the cell using a LiCoO₂-doped NiO cathode with a maximum of 0.836 V at 500 h degraded to 0.826 V at 1000 h due to a wet seal breakdown at the cathode side. The amounts of nickel precipitated in the electrolytes of the cells using modified NiO cathodes doped with CoO and LiCoO₂ after the operation for 1000 h were 1.2 and 1.4 wt.%, respectively, which were about 60% lower than that of the standard cells using pure NiO cathodes. The enhanced chemical stability of modified NiO cathodes seems to be attributed to the fact that the presence of cobalt increases the lithium content in the cathodes by converting Ni²⁺ to Ni³⁺, resulting in stabilizing the layered crystal structure.     

Study of a Li–Ni oxide mixture as a novel cathode for molten carbonate fuel cells by electrochemical impedance spectroscopy

Li–Ni oxide mixtures with high lithium content are considered to be an alternative cathode material for molten carbonate fuel cells (MCFCs). The electrochemical behaviour of Li_0.4Ni_0.6O samples has been investigated in a Li–K carbonate melt at 650 °C by electrochemical impedance spectroscopy as a function of immersion time and O₂ and CO₂ partial pressure. The impedance spectra have been interpreted using a transmission line model that includes contact impedance between reactive particles. The Li_0.4Ni_0.6O powder particles show structural changes due to high lithium leakage and low nickel dissolution from the reactive surface to the electrolyte during the first 100 h of immersion. After this time, the structure seems to be stable. The partial pressures of O₂ and CO₂ affect the processes of oxygen reduction and Li–Ni oxide oxidation. X-ray diffraction and chemical analysis performed on samples before and after the electrochemical tests have confirmed that the lithium content decreases. SEM observations reveal a reduction in grain size after the electrochemical tests.     

Electrochemical characterization of La<Subscript>0.8</Subscript>Sr<Subscript>0.2</Subscript>MnO<Subscript>3</Subscript>-coated NiO as cathodes for molten carbonate fuel cells

La_0.8Sr_0.2MnO₃ was coated on porous NiO cathode using a simple combustion process. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were employed in the cathode characterizations. The electrochemical behavior of La_0.8Sr_0.2MnO₃-coated NiO cathodes (LSM–NiO) were also evaluated in a molten 62 mol%Li₂CO₃+38 mol%K₂CO₃ eutectic at 650 °C under the standard cathode gas condition by electrochemical impedance spectroscopy (EIS). The impedance response of the NiO and LSM–NiO cathode at different immersion times is characterized by the presence of depressed semicircles in the high frequency range and an extension at low frequencies. Impedance analysis showed that the behavior of the developed cathode was similar to that of the conventional nickel oxide cathode. The LSM–NiO showed a lower dissolution and a better catalytic efficiency superior to the state-of-the-art NiO value. Thus the cathode prepared with coating method to coat La_0.8Sr_0.2MnO₃ on the surface of NiO cathode is able to reduce the solubility of NiO to lengthen the lifetime of MCFC while maintaining the advantages of NiO cathode. The LSM–NiO shows promise as an alternate cathode in molten carbonate fuel cells (MCFCs).     

Predicting NRTL binary interaction parameters from molecular simulations

A predictive approach for calculating the binary interaction parameters ( ) of the nonrandom two liquid (NRTL) local composition model is developed, combining molecular simulations with the two‐fluid theory. The binary interaction parameters are determined for the following three sets of model binary mixtures: water + methanol, methanol + methyl acrylate, and water + methyl acrylate. For each binary mixture, the interaction parameters are expressed in terms of molecular size and strength of interactions, which are in turn, calculated from molecular simulations. We show that the binary interaction parameters determined from simulations are in qualitative agreement with those estimated from regressing experimental data. The major factors that determine the binary interaction parameters are outlined based on simple thermodynamic arguments for each mixture. © 2018 American Institute of Chemical Engineers AIChE J, 64: 2758–2769, 2018     

A study on the dependence of the micro-pore configurations on the volatilization and the burn processes of the organic compounds in the matrix of molten carbonate fuel cells

The micro-pore configurations on the matrix surface were studied by SEM. The matrix of molten carbonate fuel cell (MCFC) performance was also improved by the better coordination between the reasonable radius of the micro-pores and the higher porosity of the cell matrix. The many and complicated micro-pore configurations in the cell matrix promoted the volatilization of the organic additives and the burn of polyvinyl butyral (PVB). The smooth volatilization of the organic additives and the complete burn of PVB were the significant factors for the improved MCFC performance. Oxygen diffusion controlled-burn mechanism of PVB in the cell matrix was proposed.     

A study on the start-up and performance of a kW-class molten carbonate fuel cell (MCFC) stack

A kW-class internal-manifolded molten carbonate fuel cell (MCFC) stack (52 cells) was assembled with inorganic adhesive under a suitable stacking pressure. The organic compounds in the matrices were burnt out under the conditions of slow and uniform elevation of temperature and big flow of oxygen gas in the stack. The stacking pressure dropped with elevating temperature. The output power of the stack at 150 mA cm⁻² was 1025.5 W when the reactant gas pressure and utilization were 0.5 MPa and 20%, respectively. The thermal-electrical efficiency of the stack was enhanced by increasing the pressure of the reactant. However, it was contrarily decreased when current density was increased.     

Electrochemical behaviour of Ni + Al alloy as an alternative material for molten carbonate fuel cell cathodes

This paper presents an investigation of the performance and stability for oxygen reduction on in situ oxidized Ni alloys, specially focused on 95 at % Ni + 5 at % Al and 85 at % Ni + 15 at % Al alloy electrodes in Li/Na carbonate eutectic. Test specimens of the alloys were prepared as thin film electrodes sputtered onto Au substrates. In situ oxidation of alloy electrodes and electrochemical measurements for oxygen reduction on the electrodes were performed in the free-volume melt at 923 K. It was found that the in situ oxidized Ni + Al alloys exhibit higher performance for the oxygen reduction than the NiO without Al. Electrochemical fractal analysis (EFA) revealed higher oxide film stability of the Ni + Al alloys in comparison to NiO electrodes. The surface morphology of the alloy specimen after oxidation was investigated with SEM and AFM.     

熔融碱金属碳酸盐特性及其在能源转化技术中的应用

介绍了熔融碱金属碳酸盐的物理化学特性及其在能源转化过程中的应用,包括作为催化剂、反应介质、电解质及热载体等。混合熔盐比纯组分具有更低的熔点及较高的催化活性,通过对不同碱金属碳酸盐的合理匹配可以优化其物化性能(如熔点、黏度等),从而可提高其催化活性、增强流动性及降低电极材料NiO在熔融碳酸盐中的溶解度。     

Phase equilibria and structural properties of thiophene/[Bmim][BF4]: A molecular insight from monte carlo simulations

The phase equilibria of thiophene in 1‐butyl‐3‐methylimidazolium tetrafluoroborate ([Bmim][BF₄]) is calculated by Monte Carlo simulation in Gibbs ensemble using a united atom force field. The liquid density of studied ionic liquid and the vapor pressure of thiophene in [Bmim][BF₄] were compared with corresponding experimental data reported in the literature, and a good agreement was obtained. In order to describe the solubility of thiophene in this ionic liquid, we have calculated the radial distribution functions and spatial distribution functions of thiophene/IL mixtures to study the interaction of thiophene with cations and anions of [Bmim][BF₄] in the liquid phase. The local composition concept in fluid was also examined to give further insight into the liquid structure. The results show that thiophene is well organized around the terminal carbon atom of the butyl or methyl chain attached to the imidazolium ring of cations and tends to adopt a symmetrically distribution on the anions. © 2014 American Institute of Chemical Engineers AIChE J, 60: 3916–3924, 2014     

A carbon in molten carbonate anode model for a direct carbon fuel cell

The electrochemical oxidation of carbon at the anode of a direct carbon fuel cell (DCFC) includes charge transfer steps and chemical steps. A microstructural model of carbon particle is built, in which perfect graphene stacks are taken as the basic building blocks of carbon. A modified mechanism taking account of the irreversibility of the process and supposing that the electrochemical oxidation of carbon takes place only at the edges of the graphene sheets is proposed. A Tafel type overall rate equation is deduced along with expressions of exchange current density (j₀) and activation polarization (η_act). The performance of carbon black and graphite as the fuel of DCFC is examined. It has been found that j₀ is in the range of 0.10-6.12 mA cm⁻² at 923-1123 K and η_act is in the range of 0.024-0.28 V at 923-1123 K with current density in 10-120 mA cm⁻². Analysis of the j₀, η_act values and the product composition reveals that the charge transfer steps as well as the oxygen ion absorption steps are both important for the reaction rate. The activity of the carbon material with respect to atom location is introduced to the open circuit potential difference (OCP) calculation with Nernst equation.     

无机氯化物熔盐在乏燃料干法后 处理中的应用进展

综述了无机氯化物熔盐在乏燃料后处理中的应用进展,主要介绍了LiCl-KCl熔盐在金属乏燃料中的电解精炼和熔剂萃取、LiCl-Li2O在金属氧化物或混合金属氧化物（MOX）乏燃料中的电化学还原及NaCl-2CsCl在氧化物乏燃料电化学沉积中的应用进展。展望了中国无机氯化物熔盐在干法后处理中的应用前景及发展方向。     

Two-dimensional analysis of PEM fuel cells

This study reports a two-dimensional numerical simulation of a steady, isothermal, fully humidified polymer electrolyte membrane (PEM) fuel cell, with particular attention to phenomena occurring in the catalyst layers. Conservation equations are developed for reactant species, electrons and protons, and the rate of electrochemical reactions is determined from the Butler–Volmer equation. Finite volume method is used along with the alternating direction implicit algorithm and tridiagonal solver. The results show that the cathode catalyst layer exhibits more pronounced changes in potential, reaction rate and current density generation than the anode catalyst layer counterparts, due to the large cathode activation overpotential and the relatively low diffusion coefficient of oxygen. It is shown that the catalyst layers are two-dimensional in nature, particularly in areas of low reactant concentrations. The two-dimensional distribution of the reactant concentration, current density distribution, and overpotential is determined, which suggests that multi-dimensional simulation is necessary to understand the transport and reaction processes occurring in a PEM fuel cell.     

Preliminary comparative studies of zinc and zinc oxide electrodes on corrosion reaction and reversible reaction for zinc/air fuel cells

Even though Zn/air energy system is considered to be a promising power energy source, it has been limited to be applied for an electrically rechargeable system basically due to the problem of the irreversible reaction and the corrosion reaction. In this paper a novel attempt has been made to compare the behavior of zinc electrode with a zinc oxide electrode and a modified zinc oxide electrode containing zinc oxide and lead oxide. The hydrogen overpotential is favorable in the zinc electrode, and the modified zinc oxide electrode shows the improved properties showing the more negative potential than the case of the zinc oxide electrode. Investigations of cyclic voltammogram reveal that the pure zinc electrode is irreversible, while both the zinc oxide and the modified zinc oxide electrodes are reversible. However, as far as dendrite formation is concerned there is no marked improvement in case of the zinc oxide and the modified zinc oxide electrodes.     

MCFC动态性能数值模拟

A three dimension of dynamic mathematical model of the molten carbonate fuel cell is established,in which the heat generation, mass transfer and electrochemical characteristics are described. The performance of the fuel cell including the distributions of the temperature and the velocity is predicted numerically. Then the experimental data including the output performance of the fuel cell generation system and the temperature distributions are compared. The numerical results are in agreement with the experiment results.     

直接利用生物质的化学燃料电池研究进展

近些年燃料电池技术有了长足的发展,利用燃料电池处理废弃生物质并产电是一种新型途径,可以达到废物处理、能源回收的目的。然而,受限于燃料种类、电池性能、产物分离等因素,传统的燃料电池难以直接用于处理废弃生物质。本文首先针对中低温燃料电池如碱性燃料电池、质子交换膜燃料电池的研究现状进行了综述,结果表明,碱性燃料电池在以小分子有机物作为燃料时性能良好,但是容易受到产物CO₂酸化影响;液相催化燃料电池在催化剂耐受性、生物质处理、电池功率密度等方面表现出优异的性能。然后介绍了电催化剂如过渡金属氧化物、多酸等研究现状,此类催化剂具有较强的氧化性、布朗斯特酸性和路易斯酸性等,具有很强的催化分解生物质的能力,针对液相催化剂不易分离的局限,介绍了催化剂固载化、纳米复合材料等研究进展。之后介绍了电极材料和膜材料的研究进展,碳极板因其综合性能和成本成为当前的主流选择,全氟磺酸膜性能优异,成为实验探究应用的理想材料,同时对一些复合材料的研究现状进行了简要介绍。最后,对化学燃料电池应用于生物质处理的方向进行了展望,液相催化燃料电池综合性能突出,在可处理生物质种类、催化剂循环等问题进一步优化之后,有望成为一种废弃生物质处理的新途径。     

Revisiting electrolyte thermodynamic models: Insights from molecular simulations

Pitzer and electrolyte nonrandom two‐liquid (eNRTL) models are the two most widely used electrolyte thermodynamic models. For aqueous sodium chloride (NaCl) solution, both models correlate the experimental mean ionic activity coefficient (γ_±) data satisfactorily up to salt saturation concentration, that is, ionic strength around 6 m. However, beyond 6 m, the model extrapolations deviate significantly and diverge from each other. We examine this divergence by calculating the mean ionic activity coefficient over a wide range of concentration based on molecular simulations and Kirkwood–Buff theory. The asymptotic behavior of the activity coefficient predicted by the eNRTL model is consistent with the molecular simulation results and supersaturation experimental data. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3728–3734, 2018     

吸附脱硫及分子模拟计算应用的研究进展

综述了采用各种吸附方法脱除汽油、柴油中硫的研究进展。认为天然矿物及未改性商业分子筛具有价格便宜的优点,但本身脱硫性能不是很好;改性活性炭在硫化物吸附容量方面比较优良,但机械强度不高;金属氧化物及负载金属氧化物的多孔复合材料对硫化物的选择性较高,但吸附容量不大;以过渡金属离子改性分子筛,尤其是利用π络合脱硫的研究为以后柴油深度脱硫开拓了方向。指出吸附法结合其他脱硫工艺将是深度脱硫的重要研究方向之一;分子模拟应用于吸附脱硫的研究,将为脱硫吸附剂的开发提供新的途径。     

The stability of direct carbon fuel cells with molten Sb and Sb–Bi alloy anodes

The long‐term stability of direct carbon fuel cells, based on solid oxide fuel cells with molten Sb and Sb–Bi anodes, was examined for operation with activated charcoal, rice starch, and bio‐oil fuels at 973 K. With intermittent stirring of the fuel–metal anode interface, the anode performance was stable, and reasonable power densities (～250 mW/cm²) were achieved for periods up to 250 h. With Sc‐stabilized zirconia, severe thinning of the electrolyte occurred in regions of high current flow. No electrolyte thinning was observed with yttria‐stabilized zirconia as the electrolyte operating at the same current densities. © 2012 American Institute of Chemical Engineers AIChE J, 59: 3342–3348, 2013