质子交换膜燃料电池动态建模及特性分析

通过分析质子交换膜燃料电池电压的影响因素,利用理想气体状态方程的微分形式求得氢气和氧气分压,并且结合热力学电动势及燃料电池的各种损耗,建立PEMFC的动态模型。通过对参数进行合理设定,得到PEMFC的稳态模型,其仿真结果与实验结果有较好的吻合,表明所建立模型的正确性、可操作性和有效性。利用建立的动态模型分析在载荷突变的情况下,输出电压和氢气分压的动态响应特性,从而达到准确模拟实际燃料电池系统的工作性能,评价预测燃料电池的承载能力和指导燃料电池堆操作的目的。     

Electrochemical noise of a hydrogen-air polymer electrolyte fuel cell operating at different loads

The electrochemical noise of a polymer membrane hydrogen-air fuel cell operating at different load currents was measured in serial experiments. Spectral power densities of the noise are shown to be divided into three regions. At frequencies greater than 3–10 Hz, the spectrum dependence has a constant slope of ??2 in the bilogarithmic coordinates. At frequencies 0.3–5 Hz, there is a horizontal plateau in which length is determined by the value of a load. At frequencies less than 0.3 Hz, the dependence of spectral power density has a slope of ??2. Medium-frequency plateau and high-frequency slope of spectral power densities of the noise were approximated by model RC circuits. The values of Faradic resistance and double-layer capacitance connected in parallel were obtained from the electrochemical impedance data. At load voltages higher 0.5 V, the height of the plateau was shown to be proportional to the 2.68 power of the load current value.     

聚苯胺修饰Pt/C催化剂对质子交换膜燃料电池动态响应的促进作用

将超级电容器材料聚苯胺引入电极催化剂中以缓冲燃料电池负载的变化.以硫酸为掺杂剂,将化学法合成的聚苯胺(PANI)与Pt/C超声分散混合,制成PANI-Pt/C催化剂.PANI-Pt/C的循环伏安测试和作为质子交换膜燃料电池阴极电催化剂的电池性能测试表明,PANI含量为10%时能够提高Pt/C催化剂对氧的还原动力学速度和燃料电池放电性能.电池在不同电流负载下的电压动态响应和对电池脉冲电流的动态响应以及PANI-Pt/C催化剂多电位电势阶跃计时电流测试显示,聚苯胺在催化剂中具有在瞬间电流负载时缓冲电池电压和电池大电流放电时平稳电压的作用.     

周期性负载变化提高乙醇燃料电池效率(英文)

We present a simple method to increase the efficiency of a direct ethanol fuel cell by a periodic modulation of the load(pulsed mode). The fuel cell was periodically short circuited with a resistor(1 Ω) for a few seconds(high load period) followed by a low load period of up to 100 s when the resistor was disconnected. The open circuit voltage(OCV) values before and after the short circuit of the cell showed an increase of up to 70 mV. The higher OCV was due to the oxidation and removal of strongly adsorbed CO during the electric short circuit when the electric potential of the anode was increased to be close to the cathode potential. The depoisoned anode surface was much more active directly after the short circuit. The slow decrease of the OCV observed after the short circuit was caused by the subsequent poisoning of the anode surface, which can be neutralized by another short circuit. In general, a stable increase in cell performance was obtained by repetition of the electric short circuit. The data showed that the pulse mode gave an increase in the power generated by the direct ethanol fuel cell by up to 51% and was 6% on average. It is anticipated that this mode of operation can be used also in different types of polymer electrolyte membrane fuel cells where CO poisoning is a problem, and after optimization of the parameters, a much higher gain in efficien-cy can be obtained.     

Modeling processes of thermal decomposition of hydrocarbon fuels in heated channels

We introduce a mathematical model of the nonequilibrium process of thermal decomposition of hydrocarbon fuel in heated channels of a ramjet combustion chamber cooling system. This mathematical model is based on describing the process using intermediate asymptotics formed when taking into account the equilibrium gas composition, which is determined using open source software for calculating the equilibrium state of the chemical reaction products. A procedure was introduced allowing at different stages of the process of thermal decomposition of fuel to separate kinetically irreversible and reversible chemical reactions and to exclude from consideration chemical reactions which remained incomplete in a limited size engine. We present the features of the process of thermal decomposition of liquid and solid fuels which can be used in high-speed aircraft engines.     

Effect of load-cycling amplitude on performance degradation for proton exchange membrane fuel cell

Durability is one of the critical issues to restrict the commercialization of proton exchange membrane fuel cells (PEMFCs) for the vehicle application. The practical dynamic operation significantly affects the PEMFCs durability by corroding its key components. In this work, the degradation behavior of a single PEMFC has been investigated under a simulated automotive load-cycling operation, with the aim of revealing the effect of load amplitude (0.8 and 0.2 A/cm² amplitude for the current density range of 0.1−0.9 and 0.1−0.3 A/cm², respectively) on its performance degradation. A more severe degradation on the fuel cell performance is observed under a higher load amplitude of 0.8 A/cm² cycling operation, with ∼10.5% decrease of cell voltage at a current density of 1.0 A/cm². The larger loss of fuel cell performance under the higher load amplitude test is mainly due to the frequent fluctuation of a wider potential cycling. Physicochemical characterizations analyses indicate that the Pt nanoparticles in cathodic catalyst layer grow faster with a higher increase extent of particle size under this circumstance because of their repeated oxidation/reduction and subsequent dissolution/agglomeration process, resulting in the degradation of platinum catalyst and thus the cell performance. Additionally, the detected microstructure change of the cathodic catalyst layer also contributes to the performance failure that causes a distinct increase in mass transfer resistance.     

Ba0.95Ce0.9Y0.1O3-α固体氧化物燃料电池性能

以Ba0.95Ce0.9Y0.1O3-α为固体电解质,Pt为电极,组成氢-空气燃料电池,测定了该电池600～1000℃下电流-电压特性、电极极化特性和电解质中各电荷载流子(质子、氧离子、电子空穴)迁移数及其电导率。实验表明,该电池放电性能良好,能稳定地输出电能,1000℃时的最大输出电流密度为680mA.cm^-^2。正、负Pt电极极化特性很小,放电时的电压耗损主要由电解质电阻产生。在氢-空气燃料电池条件下,Ba0.95Ce0.9Y0.1O3-α显示混合离子(质子+氧离子)导电性。随着温度升高,质子迁移数减小而氧离子迁移数增大,当温度为780℃时,质子和氧离子迁移数相同(0.46),在低于780℃时,质子电导占优势,而在高于780℃时,氧离子电导占优势。     

Performance enhancement of phosphoric acid fuel cell using phosphosilicate gel based electrolyte

Replacement of phosphoric acid electrolyte by phosphosilicate gel based electrolytes is proposed for performance enhancement of phosphoric acid fuel cell(PAFC).Phosphosilicate gel in paste form and in powder form is synthesized from tetraethoxysilane and orthophosphoric acid using sol-gel method for two different P/Si ratio of 5 and 1.5 respectively.Replacement of phosphoric acid electrolyte by phosphosilicate gel paste enhances the peak power generation of the fuel cell by 133% at 120 ℃ cell temperature;increases the voltage generation in the ohmic regime and extends the maximum possible load current.Polyinyl alcohol(PVA) is used to bind the phosphosilicate gel powder and to form the hybrid crosslinked gel polymer electrolyte membrane.Soaking the membrane with phosphoric acid solution,instead of that with water improves the proton conductivity of the membrane,enhances the voltage and power generation by the fuel cell and extends the maximum possible operating temperature.At lower operating temperature of 70 ℃,peak power produced by phosphosilicate gel polymer electrolyte membrane fuel cell(PGMFC) is increased by 40% compared to that generated by phosphoric acid fuel cell(PAFC).However,the performance of composite membrane diminishes as the cell temperature increases.Thus phosphosilicate gel in paste form is found to be a good alternative of phosphoric acid electrolyte at medium operating temperature range while phosphosilicate gel-PVA composite offers performance enhancement at low operating temperatures.     

Reaction of SO4˙⁻ with an oligomer of poly(sodium styrene sulfonate). Probing the mechanism of damage to fuel cell membranes

Clarification of the mechanism of degradation of model compounds for polymers used in polymer electrolyte fuel cells may identify intermediates that propagate damage; such knowledge can be used to improve the lifetime of fuel cell membranes, a central issue to continued progress in fuel cell technology. In proton-exchange membranes based on poly(styrene sulfonic acid), hydroxycyclohexadienyl radicals are formed after reaction with HO˙ and thought to decay to short-lived radical cations at low pH. To clarify subsequent reactions, we generated radical cations by reaction of SO(4)˙(-) with oligomers of poly(styrene sulfonic acid) (MW ≈ 1100 Da). At 295 K, this reaction proceeds with k = (4.5 ± 0.6) × 10(8) M(-1) s(-1), both at pH 2.4 and 3.4, and yields benzyl radicals with an estimated yield of ≤60% relative to [SO(4)˙(-)]. The radical cation is too short-lived to be observed: based on a benzyl radical yield of 60%, a lower limit of k > 6.8 × 10(5) s(-1) for the intramolecular transformation of the aromatic radical cation of the oligomer to a benzyl radical is deduced. Our results show that formation of the benzyl radical, an important precursor in the breakdown of the polymer, is irreversible.     

Research on Performance Decay Mechanism of Pt/C Catalyst in Long-Term ORR Test北大核心CSCD

In proton exchange membrane fuel cells,cost,performance and durability are important issues that are need to be resolved before commercialization. The main reason for fuel cell performance degradation during operation is the loss of electrochemical surface area during long-term aging or transient. These losses mainly come from the degradation of the catalyst metal and the corrosion of the carbon support. This is a continuous and irreversible process that will greatly shorten the service life of the fuel cell. In order to explore this problem,20%（mass fraction）Pt/C catalyst is prepared based on carbon carrier etched by sulfuric acid. The morphology characterization test shows that it is uniformly dispersed and uniform in particle size,which is considered as an excellent material for long-term oxygen reduction （ORR） stability test. Next,the ORR stability test method with different cyclic voltammetry （CV） cycles is used to observe its performance degradation,and a series of physical characterizations,e. g. transmission electron microscopy（TEM）,high-resolution electron microscopy（HRTEM）,X-ray photoelectron spectroscopy（XPS）and Raman spectroscopy （Raman）,are used to further intuitively analyzed the attenuation mechanism. It is reported that the reasons for the degradation of the stability of Pt/C catalysts are mainly from the dissolution,agglomeration,oxidation and migration of Pt particles and the corrosion of carbon supports. This study elucidates the source of the impact on the stability of fuel cells during operation,and provides a reference for designing high-stability commercial ORR catalysts. © 2022, Science Press (China). All rights reserved.     

Determination of polycyclic aromatic sulfur heterocycles in diesel particulate matter and diesel fuel by gas chromatography with atomic emission detection

The sulfur content of diesel fuel is of environmental concern because sulfur can facilitate the formation of diesel particulate matter (DPM) and sulfur dioxide (SO2) in the exhaust can poison catalytic converters. The US Environmental Protection Agency (EPA) has established more stringent regulations to reduce the sulfur content of diesel fuels in the near future. In this study, various types of organosulfur compounds in DPM extracts and the corresponding fuels have been determined by gas chromatography with atomic emission detection. The diesel fuels used have sulfur contents of 2284 and 433 ppm, respectively, and are labeled as high-sulfur and low-sulfur diesel fuels. The compounds identified are mainly polycyclic aromatic sulfur heterocycles (PASHs). In the fuels tested, trimethylbenzothiophenes (TMBTs), dibenzothiophenes (DBTs), and 4-methyldibenzothiophene (4-MDBT) were the most abundant sulfur compounds, while larger PASH compounds were more abundant in DPM extracts. The high-sulfur diesel fuel contained a larger proportion of PASHs with one or two rings (lighter PASHs). In DPM, the concentrations of total organic sulfur and individual PASHs are higher for the high-sulfur diesel fuel, and the relative percentage of one or two-ring PASHs is higher as well. The influence of engine load on the DPM composition was also examined. With increasing load, the PASH concentration in DPM decreased for lighter PASHs, increased for heavier PASHs, and had a bell-shaped distribution for PASHs in between.     

Degradation processes in hydrogen–air fuel cell as a function of the operating conditions and composition of membrane–electrode assemblies

The optimal composition of membrane–electrode assemblies and operating conditions of hydrogen–air fuel cells, which provide a high efficiency and stability of catalytically active cathode layers and the fuel cell as a whole are determined for commercial monoplatinum electrocatalysts on the highly dispersed carbon support containing 60–70 wt % Pt. The degradation processes in the Pt/C catalysts are studied by a complex of electrochemical methods and the methods of structural analysis.     

YSZ中温燃料电池的稳态模拟

依据同时考虑电化学及热平衡耦合的二维模拟软件 ,计算了薄膜钇稳氧化锆 (YSZ)中温燃料电池在不同工作条件下的稳态特性 .通过电流～电压关系参数进行自拟合实验 ,格点选取由平衡收敛性和计算效率而得 ,研究了不同连接体、气流流向设计等工作条件下的温度场 ,给出了不同工作温度下输出功率及电池效率与工作电压的关系 .对温度场的分析表明 :电池板内最高温度及最大温差以并流为最小 ,交叉流为最大 ,并流是最好的气流流向设计 .与以陶瓷材料作连接体相比 ,使用金属连接体能显著减小热应力和电池板内最高温度 ,受益最大的是交叉流 ,其最高温度及最大温差均小于陶瓷连接体的并流设计 .不同的气流流向对于输出功率及电池效率影响很小 ,对并流和金属连接体组合 ,给出了工程设计的燃料分布、电流密度、Nernst势及温度梯度在典型工作条件下的情形     

Performance of a polymer electrolyte fuel cell with long oxygen channel

Along-the-channel analytical model of a polymer electrolyte fuel cell is developed. The model takes into account oxygen diffusion in backing layer, diffusion and electroosmotic transport of water in membrane and oxygen depletion in a feed channel. Voltage current curve of a cell, which takes into account all these processes is obtained and expression for limiting current density is derived. The latter shows, that cell performance is described by design parameters, which are combinations of geometrical and working parameters. The region of optimal cell performance on the plane of the design parameters is determined.     

燃料电池聚合物电解质膜的研究进展

本文根据聚合物电解质膜燃料电池操作温度、使用的电解质和燃料的不同,将其分为高温质子交换膜燃料电池、低温质子换膜燃料电池、直接甲醇燃料电池和阴离子交换膜燃料电池,综述了它们所用电解质膜的最新进展.第一部分简要介绍了这4种燃料电池的优点和不足.第二部分首先介绍了Nafion膜的结构模型,并对平行柱状纳米水通道模型在介观尺度上进行了修正;接着分别对应用于不同燃料电池的改性膜的改性思路作了分析;最后讨论了用于不同燃料电池的新型质子交换膜的研究,同时列举了性能突出的改性膜和新型质子交换膜.第三部分介绍了阴离子交换膜的研究现状.第四部分对未来聚合物电解质膜的研究作了展望.     

Single fuel cell with supported LSM cathode

Single fuel cells with bilayer supported cathodes are manufactured and tested. The cathodes consist of a high-porous La_0.6Sr_0.4MnO₃ support with the thickness of approximately 1 mm and a functional composite layer with the thickness of 13?C15 ??m made of La_0.75Sr_0.2MnO₃ and 8YSZ. Voltammetric and power characteristics of single fuel cells with a supported cathode, thin-film YSZ electrolyte, and platinum cathode are determined. The conclusion as to the significant contribution into the polarization overpotential losses on the cathode is made on the basis of the measurements of electric fuel cell characteristics. It decreases significantly as a result of the supported cathode modification by praseodymium oxide. At 850°C and voltage of 0.81 V, electric power density of a fuel cell was 1.65 W/cm².     

车用燃料电池现状与电催化

本文综述了近年来车用燃料电池电催化的发展状况,分析了车用燃料电池电催化的发展趋势,重点介绍了大连化学物理研究所在燃料电池电催化方面的研究进展．指出车用燃料电池电催化的发展方向是提高现有铂基催化剂的活性,在保证车用燃料电池在变载等动态工况下的可靠性与寿命的前提下,应降低膜电极的贵金属铂用量,发展低铂／非铂电催化剂．针对车用燃料电池的使用条件,应发展抗燃料气与空气中杂质的电催化方法与抗腐蚀催化剂载体．从长远考虑,重点发展碱性聚合物膜燃料电池,拓展利于活化顺磁性氧的催化方法,有望摆脱车用燃料电池对铂催化剂的依赖．     

Microstructure and interfacial adhesion of high velocity oxy‐fuel‐sprayed MoB–CoCr alloy coating on 316L stainless steel

In this article, a newly developed MoB–CoCr alloy coating was deposited on 316L stainless steel substrate by high velocity oxy‐fuel thermal spraying process. The microstructures and interfacial adhesion of the alloy coating were determined by scanning electron microscopy, X‐ray diffraction and three‐point bending. The results show that the coating consisted of ternary transition metal boride matrix phases (CoMo₂B₂, CoMoB) and a little amount of binary borides (MoB and CrB), the former composed of partially amorphous phase. The formation of the amorphous phase was attributed to the high cooling rates of molten droplets and the proper powder compositions. In the interfacial adhesion measurement, the delamination of the coating is induced during the three‐point bending test, and the interfacial fracture toughness is analyzed using a finite element analysis model. The critical load is determined by comparing the load versus deflection curves obtained by finite element analysis under assumed no crack conditions with the experimental data, and other inputs are determined by test. Copyright © 2009 John Wiley & Sons, Ltd.     

Study of degradation of membrane-electrode assemblies of hydrogen-oxygen (air) fuel cell under the conditions of life tests and voltage cycling

The degradation processes of HiSPEC 9100 (60% Pt/C) and 13100 (70% Pt/C) cathodic monoplatinum catalysts, which were tested under the model conditions and in the composition of membrane-electrode assemblies (MEA) of hydrogen-air and hydrogen-oxygen fuel cells, are studied. It is shown that, in all cases, the main reason for a decrease in the catalyst activity was a decrease in its surface area, which was caused by the coarsening of platinum nanoparticles, irreversible oxidation of a fraction of active centers, and the destruction of the catalyst due to the carbon support oxidation. The results of electrochemical measurements are supplemented with the structural investigations by the methods of transmission electron microscopy (TEM), X-ray diffraction analysis (XRD), and X-ray photoelectron spectroscopy (XPS). It is found that the degradation processes of MEA in the accelerated stress tests (AST) are similar to those in the long-term life tests. With respect to a decrease in the catalyst active surface area, the application of 2500 cycles in the voltage range of 0.6 to 1.2 V in the AST is equivalent to the life tests for 1010 h. During the fuel cell operation, the destruction of polymer electrolyte proceeds along with the catalyst degradation. This leads to a decrease in the ion-exchange capacity of the membrane and ionomer in the composition of cathode active layer.     

固相法合成中温固体电解质La-Bi-Al-O和La-Bi-Al-Zn-O系列材料

采用固相合成法合成了Ｌａ－Ｂｉ－Ａｌ－Ｏ和Ｌａ－Ｂｉ－Ａｌ－Ｚｎ－Ｏ系列材料，确定了其物相为ＬａＡｌＯ３，ＢｉＡｌＯ３和Ａｌ４Ｂｉ２Ｏ９的混合相。在Ｌａ－Ｂｉ－Ａｌ－Ｚｎ－Ｏ系列材料中，Ｚｎ＾２＋加入到ＬａＡｌＯ３和ＢｉＡｌＯ３的晶格中，且可使材料的导电率进一步增高。