One-dimensional Dynamic Modeling and Simulation of a Planar Direct Internal Reforming Solid Oxide Fuel Cell

This article aims to investigate the transient behavior of a planar direct internal reforming solid oxide fuel cell(DIR-SOFC) comprehensively.A one-dimensional dynamic model of a planar DIR-SOFC is first developed based on mass and energy balances,and electrochemical principles.Further,a solution strategy is presented to solve the model,and the International Energy Agency(IEA) benchmark test is used to validate the model.Then,through model-based simulations,the steady-state performance of a co-flow planar DIR-SOFC under specified initial operating conditions and its dynamic response to introduced operating parameter disturbances are studied.The dynamic responses of important SOFC variables,such as cell temperature,current density,and cell voltage are all investigated when the SOFC is subjected to the step-changes in various operating parameters including both the load current and the inlet fuel and air flow rates.The results indicate that the rapid dynamics of the current density and the cell voltage are mainly influenced by the gas composition,particularly the H2 molar fraction in anode gas channels,while their slow dynamics are both dominated by the SOLID(including the PEN and interconnects) temperature.As the load current increases,the SOLID temperature and the maximum SOLID temperature gradient both increase,and thereby,the cell breakdown is apt to occur because of excessive thermal stresses.Changing the inlet fuel flow rate might lead to the change in the anode gas composition and the consequent change in the current density distribution and cell voltage.The inlet air flow rate has a great impact on the cell temperature distribution along the cell,and thus,is a suitable manipulated variable to control the cell temperature.

Numerical simulation of a direct internal reforming solid oxide fuel cell using computational fluid dynamics method

A detailed mathematical model of a direct internal reforming solid oxide fuel cell(DIR-SOFC) incorporating with simulation of chemical and physical processes in the fuel cell is presented. The model is developed based on the reforming and electrochemical reaction mechanisms,mass and energy conservation,and heat transfer. A computational fluid dynamics(CFD) method is used for solving the complicated multiple partial differential equations(PDEs) to obtain the numerical approximations. The resulting distributions of chemical species concentrations,temperature and current density in a cross-flow DIR-SOFC are given and analyzed in detail. Further,the influence between distributions of chemical species concentrations,temperature and current density during the simulation is illustrated and discussed. The heat and mass transfer,and the kinetics of reforming and electrochemical reactions have significant effects on the parameter distributions within the cell. The results show the particular characteristics of the DIR-SOFC among fuel cells,and can aid in stack design and control.

Modified electronic structure and enhanced hydroxyl adsorption make quaternary Pt-based nanosheets efficient anode electrocatalysts for formic acid-/alcohol-air fuel cells

Surface/interface engineering of a multimetallic nanostructure with diverse electrocatalytic properties for direct liquid fuel cells is desirable yet challenging.Herein,using visible light,a class of quaternary Pt_(1)Ag_(0.1)Bi_(0.16)Te_(0.29)ultrathin nanosheets is fabricated and used as high-performance anode electrocatalysts for formic acid-/alcohol-air fuel cells.The modified electronic structure of Pt,enhanced hydroxyl adsorption,and abundant exterior defects afford Pt_(1)Ag_(0.1)Bi_(0.16)Te_(0.29)/C high intrinsic anodic electrocatalytic activity to boost the power densities of direct formic acid-/methanol-/ethanol-/ethylene glycol-/glycerol-air fuel cells,and the corresponding peak power density of Pt_(1)Ag_(0.1)Bi_(0.16)Te_(0.29)/C is respectively 129.7,142.3,105.4,124.3,and 128.0 mW cm^(-2),considerably outperforming Pt/C.Operando in situ Fourier transform infrared reflection spectroscopy reveals that formic acid oxidation on Pt_(1)Ag_(0.1)Bi_(0.16)Te_(0.29)/C occurs via a CO_(2)-free direct pathway.Density functional theory calculations show that the presence of Ag,Bi,and Te in Pt_(1)Ag_(0.1)Bi_(0.16)Te_(0.29)suppresses CO^(*)formation while optimizing dehydrogenation steps and synergistic effect and modified Pt effectively enhance H_(2)O dissociation to improve electrocatalytic performance.This synthesis strategy can be extended to 43 other types of ultrathin multimetallic nanosheets(from ternary to octonary nanosheets),and efficiently capture precious metals(i.e.,Pd,Pt,Rh,Ru,Au,and Ag)from different water sources.

Stable NiPt-Mo_(2)C active site pairs enable boosted water splitting and direct methanol fuel cell

Sluggish kinetics of methanol oxidation reaction(MOR)and alkaline hydrogen evolution reaction(HER)even on precious Pt catalyst impede the large-scale commercialization of direct methanol fuel cell(DMFC)and water electrolysis technologies.Since both of MOR and alkaline HER are related to water dissociation reaction(WDR),it is reasonable to invite secondary active sites toward WDR to pair with Pt for boosted MOR and alkaline HER activity on Pt.Mo_(2)C and Ni species are therefore employed to engineer NiPt-Mo_(2)C active site pairs,which can be encapsulated in carbon cages,via an in-situ self-confinement strategy.Mass activity of Pt in NiPt-Mo_(2)C@C toward HER is boosted to11.3 A mg_(pt)^(-1),33 times higher than that of Pt/C.Similarly,MOR catalytic activity of Pt in NiPt-Mo_(2)C@C is also improved by 10.5 times and the DMFC maximum power density is hence improved by 9-fold.By considering the great stability,NiPt-Mo_(2)C@C exhibits great practical application potential in DMFCs and water electrolysers.

The Catalysis of NAD^+ on Methanol Anode Oxidation Electrode for Direct Methanol Fuel Cell

A tentative idea of developing a liquid-catalytic system on methanol anode oxidation was proposed by analyzing the characteristics of methanol anode oxidation in direct methanol fuel cell. The kinetics of methanol oxidation at a glassy carbon electrode in the presence of nicotinamide adenine dinucleotide (NAD +) was investigated. It is found that the current density of methanol oxidation increases greatly and the electrochemical reaction impedance reduces obviously in the presence of NAD + compared with those in the absence of NAD +. The catalytic activity of NAD + is sensitive to temperature. When the temperature preponderates over 45℃, NAD + is out of function of catalysis for methanol oxidation, which is probably due to the denaturation of NAD + at a relatively high temperature.

Carbon Nanotubes Supported Pt-Ru-Ni as Methanol Electro-Oxidation Catalyst for Direct Methanol Fuel Cells

Carbon nanotubes （CNTs） supported Pt-Ru and Pt-Ru-Ni catalysts were prepared by chemical reduction of metal precursors with sodium borohydride at room temperature. The crystallographic properties and composition of the catalysts were characterized by X-ray diffraction （XRD） and energy dispersive X-ray （EDX） analysis, and the catalytic activity and stability for methanol electro-oxidation were measured by electrochemical impedance spectroscopy （EIS）, linear sweep voltammetries （LSV）, and chronoamperometry （CA）. The results show that the catalysts exhibit face-centered cubic （fcc） structure. The particle size of Pt-Ru-Ni/CNTs catalyst is about 4.8 nm. The catalytic activity and stability of the Pt-Ru-Ni/CNTs catalyst are higher than those of Pt-Ru/CNTs catalyst.

Synthesis and characterization of Pt-MoO_x-TiO_2 electrodes for direct ethanol fuel cells

To enhance the CO-tolerance performance of anode catalysts for direct ethanol fuel cells,carbon nanotubes were modified by titanium dioxide （donated as CNTs@TiO2） and subsequently served as the support for the preparation of Pt/CNTs@TiO2 and Pt-Mo/CNTs@TiO2 electrocatalysts via a UV-photoreduction method.The physicochemical characterizations of the catalysts were carried out by using X-ray diffraction （XRD）,transmission electron microscopy （TEM）,X-ray photoelectron spectroscopy （XPS）,and infrared spectroscopy of adsorbed probe ammonia molecules.The electrocatalytic properties of the catalysts for methanol oxidation were investigated by the cyclic voltammetry technique.The results show that Pt-Mo/CNTs@TiO2 electrode exhibits the highest performance in all the electrodes.It is explained that,the structure,the oxidation states,and the acid-base properties of the catalysts are influenced due to the strong interaction between Ti and Mo species by adding TiO2 and MoOx to the Pt-based catalysts.

Functionalised Poly(Vinyl Alcohol)/Graphene Oxide as Polymer Composite Electrolyte Membranes

Crosslinked poly(vinyl alcohol)(PVA)based composite films were prepared as polyelectrolyte membranes for low temperature direct ethanol fuel cells(DEFC).The membranes were functionalised by means of the addition of graphene oxide(GO)and sulfonated graphene oxide(SGO)and crosslinked with sulfosuccinic acid(SSA).The chemical structure was corroborated and suitable thermal properties were found.Although the addition of GO and SGO slightly decreased the proton conductivity of the membranes,a significant reduction of the ethanol solution swelling and crossover was encountered,more relevant for those functionalised with SGO.In general,the composite membranes were stable under simulated service conditions.The addition of GO and SGO particles permitted to buffer the loss and almost retain similar proton conductivity than prior to immersion.These membranes are alternative polyelectrolytes,which overcome current concerns of actual commercial membranes such as the high cost or the crossover phenomenon.

Ca_(2)Fe_(2)O_(5)催化剂对半焦基DC-SOFC性能的影响

半焦与CO_(2)的气化反应速率是影响半焦燃料基DC-SOFC电池性能的关键。为提高半焦的CO_(2)气化反应性,采用柠檬酸溶胶-凝胶法制备了具有钙钛矿结构的Ca_(2)Fe_(2)O_(5)催化剂,用SEM、XRD、XPS、低温氮气吸脱附等分析手段研究了Ca_(2)Fe_(2)O_(5)催化剂的形貌和结构,采用热重分析实验研究Ca_(2)Fe_(2)O_(5)催化剂对半焦燃料的CO_(2)气化反应催化活性;在Ag-GDC|YSZ|GDC-Ag电解质支撑电池系统上,研究了添加Ca_(2)Fe_(2)O_(5)催化剂对半焦燃料基DC-SOFC输出性能的影响。结果表明,随着催化剂焙烧温度的提高,Ca_(2)Fe_(2)O_(5)催化剂晶粒尺寸逐渐增大、比表面积降低,750℃焙烧的催化剂具有良好的分散性、颗粒尺寸约为0.1μm,在半焦的CO_(2)气化反应中催化作用最好;相较于CaO和Fe2O3,Ca_(2)Fe_(2)O_(5)催化剂结构中吸附氧浓度更高,在半焦的CO_(2)气化反应中表现出更为优异的催化活性;Ca_(2)Fe_(2)O_(5)催化剂的循环稳定性取决于催化剂结构的热稳定性,其循环使用时活性降低主要归因于半焦燃料中无机灰分的包裹。催化剂对DC-SOFC输出性能影响表明,当半焦中添加10%的Ca_(2)Fe_(2)O_(5)催化剂时,电池的峰值功率密度从15.3 mW/cm^(2)增大到23.7 mW/cm^(2);EIS分析表明阳极传质阻力是影响DC-SOFC输出性能和燃料利用率的主要因素,降低灰分、催化剂累积带来的传质阻力可有效提高电池寿命和燃料利用率。

石墨烯负载Pt催化剂的制备及对甲酸的电催化氧化

采用恒电位电化学还原技术制得石墨烯电极,然后采用循环伏安方法在石墨烯基体上电沉积一层Pt纳米微粒.采用电化学测试技术研究Pt/石墨烯电极材料的电子传递性能及对甲酸电催化氧化性能.相对于商用Pt电极材料,Pt纳米微粒/石墨烯电极材料对甲酸表现出优异的电催化氧化活性,氧化峰电流显著提高.该种石墨烯负载Pt催化剂有望用作直接甲酸燃料电池的优良电极材料.

光辅助直接甲醇燃料电池阳极催化剂的研究进展

直接甲醇燃料电池(DMFCs)因其能够在较低工作温度下提供清洁、可持续能源方面的潜力而备受关注,但阳极缓慢的甲醇氧化反应(MOR)限制了其商业化应用。光辅助直接甲醇燃料电池(PMFCs)能利用光电耦合机制加速MOR过程,实现甲醇的化学能高效转化为电能,为开发高效、可持续的能源转换系统带来了巨大希望。本文首先简要回顾了PMFCs的背景、意义和在能源研究中的价值。从PMFCs的基本结构组成和酸碱介质下甲醇光电催化氧化的基本路径出发,总结了PMFCs阳极光电催化剂的研究进展。重点针对不同类型的PMFCs阳极光电催化剂,讨论光辅助下的MOR增强机制,如催化剂的尺寸效应、晶面效应、吸光性能、导电性以及表面等离激元共振(SPR)效应等方面的影响。PMFCs未来需要重点关注的研究方向是深入理解PMFCs的光电耦合机制和PMFCs阳极催化剂的构效关系,以及解决实际二电极系统下PMFCs光阳极的设计问题。

Rare earth metal oxides as BH_4^--tolerance cathode electrocatalysts for direct borohydride fuel cells

Rare earth metal oxides（REMO） as cathode electrocatalysts in direct borohydride fuel cell（DBFC） were investigated.The REMO electrocatalysts tested showed favorable activity to the oxygen electro-reduction reaction and strong tolerance to the attack of BH 4-in alkaline electrolytes.The simple membraneless DBFCs using REMO as cathode electrocatalyst and using hydrogen storage alloy as anodic electrocatalyst exhibited an open circuit of about 1 V and peak power of above 60 mW/cm 2.The DBFC using Sm 2 O 3 as cathode electrocatalyst showed a relatively better performance.The maximal power density of 76.2 mW/cm 2 was obtained at the cell voltage of 0.52 V.

固体氧化物燃料电池直接内重整的模型研究进展

固体氧化物燃料电池(SOFCs)是一种通过电化学氧化反应直接将化学能高效率地转化为电能的装置,在大规模发电、联产以及一体化燃料升级等可再生能源系统领域具有广阔的市场前景。为进一步拓宽SOFCs的应用场景,降低运行成本,直接内重整(DIR)技术可将CH4等烷烃类物质在阳极催化生成H2,减少了燃料预处理要求且提高了转化效率,是目前SOFCs研究领域的热点之一。为了优化该技术的系统设计和操作条件,模型模拟的研究可显著减少实验工作量,并为其提供理论支撑和指导性建议。通过DIR-SOFC系统的模型模拟,结合场分布、动力学参数等,可以量化评估系统内的反应,从而了解其物理、化学过程的复杂性。本文总结了DIR-SOFC建模工作的现状,介绍了体积平均模型和针对微观结构的模型;重点讨论多尺度数学模型,对现有研究中的反应动力学过程描述、“能量-质量-动量”平衡方程、“1D-2D-3D”DIR-SOFC单元描述等进行了综述,能更好地评估变量对DIR的影响;对DIR-SOFC模型中不同液体燃料的重整反应及相关的反应动力学参数进行总结;指出现有模型的不足,并对DIR-SOFC系统模型的未来发展进行展望,使模型更加精准。

Effects of CeO_(2)pre-calcined at different temperatures on the performance of Pt/CeO_(2)-C electrocatalyst for methanol oxidation reaction

Pt/CeO_(2)-C catalysts with CeO_(2)pre-calcined at 300-600 ℃were synthesized by combining hydrothermal calcination and wet im-pregnation.The effects of the pre-calcined CeO_(2)on the performance of Pt/CeO_(2)-C catalysts in methanol oxidation were investigated.The Pt/CeO_(2)-C catalysts with pre-calcined CeO_(2)at 300-600 ℃showed an average particle size of 2.6-2.9 nm and exhibited better methanol elec-tro-oxidation catalytic activity than the commercial Pt/C catalyst.In specific,the Pt/CeO_(2)-C catalysts with pre-calcined CeO_(2)at 400 ℃dis-played the highest electrochemical surface area value of 68.14 m2·g−1 and If/Ib ratio(the ratio of the forward scanning peak current density(If)and the backward scanning peak current density(Ib))of 1.26,which are considerably larger than those(53.23 m2·g−1 and 0.79,respectively)of the commercial Pt/C catalyst,implying greatly enhanced CO tolerance.

A new catalyst for urea oxidation: NiCo2S4 nanowires modified 3D carbon sponge

Urea oxidation is a significant reaction for utilizing urea-rich wastewater or human urine as sustainable power sources which can ease the water eutrophication while generate electricity. A direct urea-hydrogen peroxide fuel cell is a new kind of fuel cell employing urea as fuel and hydrogen peroxide as oxidant which possesses a larger cell voltage. Herein, this work tries to promote the kinetics process of urea oxidation by preparing low-cost and high-efficient NiCo2S4 nanowires modified carbon sponge electrode. The carbon sponge used in this work with a similar three-dimensional multi-channel structure to Ni foam, is prepared by carbonizing recycled polyurethane sponge which is also a process of recycling waste. The performance of the prepared catalyst in an alkaline solution is investigated in a three-electrode system.With the introduction of Co element to the catalyst, a reduced initial urea oxidation potential and a high performance are obtained. Furthermore, a direct urea-hydrogen peroxide fuel cell is assembled using the NiCo2S4 nanowires modified carbon sponge anode. Results indicate that the prepared catalyst provides a chance to solve the current problems that hinder the development of urea electrooxidation(high initial urea oxidation potential, low performance, and high electrode costs).

Pt-Containing Ag_2S-Noble Metal Nanocomposites as Highly Active Electrocatalysts for the Oxidation of Formic Acid

Nanocomposites with synergistic effect are of great interest for their enhanced properties in a given application. Herein, we reported the high catalytic activity of Pt-containing Ag2S-noble metal nanocomposites in formic acid oxidation, which is a key reaction in direct formic acid fuel cell. The electrochemical measurements including voltammograms and chronoamperograms are used to characterize the catalytic property of Pt-containing nanocomposites for the oxidation of formic acid. In view of the limited literatures on using nanocomposites consisting of semiconductor and noble metals for catalyzing the reactions of polymer electrolyte membrane-based fuel cells, this study provides a helpful exploration for expanding the application of semiconductor-noble metal nanocomposites.

The Catalysis of NAD^+, NADP^+ and Nicotinic Amide for Methanol Electrooxidation at Platinum Electrode

A group of liquid catalysts composed of nicotinic amide functioning on the anode of DMFC were investigated at a Pt eleetrode, which were nicotinic amide, nicotinamide adenine dinucleotide （ NAD^＋ ） and its phosphate （ NAD （ P ） ^＋ ）. The kinetics of methanol anode oxidation in the three reaction systems was compared by measuring poteatiodynarnic current-potential curves and AC impedances. The experimeatal results show that the dynamic behavior of methanol oxidation at a Pt electrode has been changed with adding the three substances. The influence of temperature on the catalysis of these coenzymes and nicotinic amicle was discussed by comparing the AC impedances spectra of methanol oxidation at differeat temperatures.

Methanol Oxidation over TiO_2-modified Multi-walled Carbon Nanotubes Supported Pt-Mo Electrocatalyst

In order to develop a novel and high-performance catalytic material for direct methanol fuel cells（DMFC）, molybdenum oxide as a co-catalyst with Pt on multi-walled carbon nanotubes which were modified by titanium dio-xide（denoted as CNTs@TiO2） was investigated. The physicochemical characterizations of the catalysts were carried out via X-ray diffraction（XRD）, transmission electron microscopy（TEM） and X-ray photoelectron spectroscopy（XPS）. Cyclic voltammetry（CV） showed that the CO-tolerance performance increased in the sequence of Pt/CNTs Pt/CNTs@TiO2Pt-Mo/CNTs@TiO2. The improved CO-tolerance performance of the Pt-Mo/CNTs@TiO2 catalyst can be attributed to the combined beneficial effects of highly dispersed Pt nanoparticles on the CNTs, the existence of oxygen holes in the MoO3 layer structure and the oxidation capability of TiO2.

Two-dimensional PtRu Nanoclusters Carbon Based Electrocatalysts for Methanol Oxidation

A novel method to prepare an electrocatalyst with a new structure and high catalytic performance was reported. Two-dimensional（2 D） PtRu nanoclusters have been successfully deposited on graphene oxide and carbon black supports. Compared with the commercial 3 D E-TEK PtRu samples, the prepared 2 D PtRu composites have larger electrochemically active surface area and display much higher catalytic activity toward methanol oxidation reaction. The preparation method mainly includes the following procedures： oxidation of carbon matrix, Pb^（2＋） adsorption on the surface of carbon support, Pb^（2＋） electrochemical reduction and galvanic displacement of Pb^0 by Pt^（2＋） and Ru^（3＋）. The method developed in this study could be viable for solving the problem of low electrocatalytic activity in direct methanol fuel cell anodes.

Rhodium Nanoparticle-Loaded Carbon Black Electrocatalyst for the Glycerol Oxidation Reaction in Alkaline Medium

Rhodium nanoparticle-loaded carbon black (Rh/CB) was prepared by a wet method, and its activity and durability for glycerol oxidation reaction (GOR) in alkaline medium were compared with Pt, Pd and Au nanoparticle-loaded CB (Pt/CB, Pd/CB and Au/CB). In the cyclic voltammogram of the Rh/CB electrode, the redox waves due to hydrogen adsorption/desorption and the surface OH monolayer formation/reduction were observed at more negative potentials than the Pt/CB and Pd/CB electrodes. The onset and peak potentials of the GOR current densities for the Rh/CB electrode were ca. –0.55 and –0.30 V vs. Hg/HgO, respectively, which were 0.10 and 0.20 V more negative than the Pt/CB electrode whose GOR activity was the best, indicating that Rh was a fascinating metal for reducing the overpotential for GOR. In the electrostatic electrolysis with the Rh/CB and Pt/CB electrodes, the decrease in the GOR current density in the former with time was suppressed compared to that in the latter, suggesting that the tolerance to poisoning for the Rh/CB electrode was superior to that for the Pt/CB electrode.