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1.
甲醇溶液浓度对于直接甲醇燃料电池(DMFC)的性能具有重要影响。 本文旨在建立一种能在电源系统中有效控制甲醇浓度的策略。 通过构建电池内甲醇物料守恒和热守恒方程,确定了基于电量和温度这两个参数的甲醇浓度控制策略。 通过测试温度-浓度关系验证了控制策略的可行性。 结果表明,采用该策略,DMFC电源系统稳定运行超过420 min;合适的甲醇浓度范围为0.70~0.87 mol/L。 该策略完成了甲醇浓度控制的目标,并将在电源系统中发挥重要作用。 相似文献
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采用交流阻抗法(EIS)研究了直接甲醇燃料电池(DMFC)放电状态下的动态电化学行为及内部作用机理. 通过L1R1[QR2(L2R3)]形式的等效电路对其阻抗图谱进行了较好的模拟解析, 研究结果表明, 高频电感(L1)相关于EIS的测量过程; 系统电阻(R1)和电荷转移电阻(R2)随工作电流的升高均呈下降趋势, 但传质状况对其具有一定干扰; 低频电感(L2)和低频电阻(R3)随电流的升高均逐渐降低, 这共同反映出阳极甲醇的电氧化行为; 电极反应驱动力和内部传质共同决定常相位角元件Q的变化规律, 随着放电电流的升高, 电池内部表现出了由理想电容到浓差极化的中间过渡过程. 相似文献
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通过测定甲醇渗透率,详细研究了阳极支撑层的聚四氟乙烯(PTFE)含量对全被动式直接甲醇燃料电池(DMFC)甲醇传质和电池性能的影响。 膜电极集合体均使用相同的阳极催化层,膜和阴极。 实验结果表明,随着阳极支撑层PTFE含量的提高,甲醇渗透速率明显减小。 其含量较高时,甲醇传质阻力较大,会导致电池在很低的电流密度下就出现传质控制区。 采用PTFE质量分数为40%的支撑层时,DMFC以9 mol/L甲醇为燃料最大功率密度可达32×10-3 W/cm2,也进一步证明了适当提高阳极支撑层的憎水性,既有助于减少甲醇的渗透,又缓解了阴极的“水淹”问题。 相似文献
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直接甲醇燃料电池Pt-Ru/C催化剂的稳定性 总被引:3,自引:2,他引:1
采用单电池寿命测试和电化学快速老化两种方法考察了直接甲醇燃料电池阳极电催化剂Pt-Ru/C的稳定性,研究了电池实际运行条件下催化剂微观形貌的变化对电池性能的影响. 结果表明,Pt-Ru/C催化剂做成膜电极后,粒径由2.8 nm增大到3.8 nm,催化剂的粒径随放电时间的延长有增大的趋势,连续放电320 h,粒径增大到5.8 nm. 采用电化学方法能够快速地评价催化剂的稳定性,大大缩短催化剂稳定性评价的周期,有利于催化剂的制备和筛选. 相似文献
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运用顺序注射分析技术,完成了样品的在线预处理,并采用固定化酶化学发光检测法测定甲醇的浓度,建立了一种在线监测甲醇酵母发酵诱导阶段发酵液中甲醇浓度的新方法。在选定的最佳条件下,甲醇浓度在0%~1.0%(V/V)范围内与化学发光强度呈良好的线性关系(R=0.9995),相对标准偏差(RSD)为1.9%(n=11),72 h内RSD为5.0%(0.2%甲醇溶液)。该法可在线自动完成过滤、稀释、测定等操作,分析速度快,长期稳定性高,能满足在线监测甲醇酵母发酵液中甲醇浓度的要求。 相似文献
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研究了CaCl2、LiCl和Ca(NO3)2在甲醇溶液中的荧光光谱,并对溶液中可能的团簇构型采用密度泛函理论和含时(TD)密度泛函理论中的B3LYP方法进行结构优化和激发能计算.实验结果表明CaCl2和LiCl与甲醇形成了具有荧光性质的簇合物,且随着CaCl2和LiCl浓度的增加溶液的荧光强度整体呈增强趋势,而Ca(NO3)2与甲醇相互作用使甲醇发生荧光猝灭.理论计算得到盐/甲醇溶液中可能存在多种簇合物,但能使甲醇溶液荧光增强的团簇构型主要为[CaCl(CH3OH)n]+和LiCl(CH3OH)n,而NO3-与甲醇通过氢键作用形成簇合物的振荡强度几乎为零,解释了NO3-使甲醇发生荧光猝灭的现象. 相似文献
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Masayuki Takeguchi Takako Furuto Daisuke Sugimori Ichiro Okura 《Applied biochemistry and biotechnology》1997,68(3):143-152
Methylosinus trichosporium OB3b is a methanotrophic bacterium containing methane mono-oxygenase, catalyzing hydroxylation of methane to methanol. When
methane is oxidized, the product is subsequently oxidized by methanol dehydrogenase contained in the same bacterium. To prevent
further oxidation of methanol, the cell suspension was treated by cyclopropanol, an irreversible inhibitor for methanol dehydrogenase,
leading to extracellular methanol accumulation. However, the reaction was terminated at approx 3 h with a final methanol concentration
below 2.96 mmol/g dry cell. The methanol production efficiency (the ratio of the produced methanol per methane consumption)
was 2.90%. By selecting the culture conditions and the reaction conditions, the reaction continued for 100 h, resulting in
a methanol concentration of 152 mmol/g dry cell. This level was 51 times higher than that of the conventional reaction, and
the methanol production efficiency was 61%. 相似文献
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生物质气催化合成甲醇的研究 总被引:11,自引:6,他引:11
在高压微型反应装置上进行了生物质气合成甲醇的研究。利用组成为H2/CO/CO2
/N2(体积比)=52.5/21.5/22.8/3.2 的富CO2原料气考察了不同温度、压力和空速条件时甲醇的时空产率和质量分数。结果表明,在所考察的范围内,甲醇的产率和质量分数在260 ℃达到最大。产率和质量分数随反应压力升高而增大,空速增加使产率增大,甲醇的质量分数降低。当p=4 MPa,t=260 ℃,WHSV=5 280 h-1时, 甲醇的时空产率为0.79 g·(mL·h)-1,质量分数为96.2%,与工业合成气相比,分别下降25.8%和1.64%。 相似文献
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The CO2 in the cathode exhaust of a liquid feed direct methanol fuel cell (DMFC) has two sources: methanol diffuses through the membrane electrode assembly (MEA) to the cathode where it is catalytically oxidized to CO2; additionally, a portion of the CO2 produced at the anode diffuses through the MEA to the cathode. The potential-dependent CO2 exhaust from the cathode was monitored by online electrochemical mass spectrometry (ECMS) with air and with H2 at the cathode. The precise determination of the crossover rates of methanol and CO2, enabled by the subtractive normalization of the methanol/air to the methanol/H2 ECMS data, shows that methanol decreases the membrane viscosity and thus increases the diffusion coefficients of sorbed membrane components. The crossover of CO2 initially increases linearly with the Faradaic oxidation of methanol, reaches a temperature-dependent maximum, and then decreases. The membrane viscosity progressively increases as methanol is electrochemically depleted from the anode/electrolyte interface. The crossover maximum occurs when the current dependence of the diffusion coefficients and membrane CO2 solubility dominate over the Faradaic production of CO2. The plasticizing effect of methanol is corroborated by measurements of the rotational diffusion of TEMPONE (2,2,6,6-tetramethyl-4-piperidone N-oxide) spin probe by electron spin resonance spectroscopy. A linear inverse relationship between the methanol crossover rate and current density confirms the absence of methanol electro-osmotic drag at concentrations relevant to operating DMFCs. The purely diffusive transport of methanol is explained in terms of current proton solvation and methanol-water incomplete mixing theories. 相似文献
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针对空气自呼吸式直接甲醇燃料电池甲醇易渗透和阴极易水淹的特点,通过对催化层催化剂载量、阴极微孔层、阳极微孔层和膜等因素进行调控,对膜电极结构和性能的进行了优化.结果表明,使用高载量催化剂能有效降低甲醇渗透,但载量过高会引起传质阻力.当阳极微孔层PTFE含量为30%(bymass)时,可以有效促进CO2的均一析出,从而降低甲醇浓度梯度,减小甲醇透过.综合考虑甲醇渗透和阴极自返水,经优化后所得MEA在室温时自呼吸工作条件下,比功率密度达到33mW·cm-2,最优甲醇工作浓度为4mol·L-1. 相似文献
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Nicholas W. DeLuca Yossef A. Elabd 《Journal of Polymer Science.Polymer Physics》2006,44(16):2201-2225
The direct methanol fuel cell (DMFC) has the potential to replace lithium‐ion rechargeable batteries in portable electronic devices, but currently experiences significant power density and efficiency losses due to high methanol crossover through polymer electrolyte membranes (PEMs). Numerous publications document the synthesis and characterization of new PEMs for the DMFC. This article reviews this research, transport phenomena in PEMs, and experimental techniques used to evaluate new PEMs for the DMFC. Although many PEMs do not show significant improvements over Nafion®, the benchmark PEM in DMFCs, experimental results show that several new PEMs exhibit lower methanol crossover at similar proton conductivities and/or higher DMFC power densities. These results and recommendations for future research are discussed. © 2006 Wiley Periodicals, Inc. J Polym Sci Parts B: Polym Phys 44: 2201–2225, 2006 相似文献
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Guo-Bin Jung Cheng-Hsin Tu Pei-Hung Chi Ay Su Fang-Bor Weng Yur-Tsai Lin Yu-Chun Chiang Chi-Yuan Lee Wei-Mon Yan 《Journal of Solid State Electrochemistry》2009,13(9):1455-1465
An experimental and simulation research had been performed to investigate the performance as well as the flow distribution
in the cathode flow field in the case of direct methanol fuel cells (DMFCs). The gas was well distributed in serpentine flow
field, whereas stagnation of the gas was observed in parallel flow field. These would contribute to the cell performance greatly
due to mass transfer effect when the cells start operating. In addition, the durability test of DMFC was drastically affected
in parallel flow field due to poor ability to drain flooded water produced electrochemically at cathode and crossover from
anode. In addition, pressure drops of different flow fields were also investigated to evaluate their contribution and feasibility
as an economic application for DMFC. DMFC with serpentine flow field featuring higher pressure difference resulted in a larger
parasitic energy demand. However, the optimal flow field designs are needed to balance the performance and pressure loss to
achieve a uniform fluid distribution and simultaneously minimize energy demand for mass transport. Consequently, flow field
with grid pattern appears to be the optimal design for the DMFC cathode. 相似文献
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Hayley A. Every Michael A. Hickner James E. McGrath Thomas A. Zawodzinski Jr. 《Journal of membrane science》2005,250(1-2):183-188
Methanol diffusion in two polymer electrolyte membranes, Nafion 117 and BPSH 40 (a 40% disulfonated wholly aromatic polyarylene ether sulfone), was measured using a modified pulsed field gradient NMR method. This method allowed for the diffusion coefficient of methanol within the membrane to be determined while immersed in a methanol solution of known concentration. A second set of gradient pulses suppressed the signal from the solvent in solution, thus allowing the methanol within the membrane to be monitored unambiguously. Over a methanol concentration range of 0.5–8 M, methanol diffusion coefficients in Nafion 117 were found to increase from 2.9 × 10−6 to 4.0 × 10−6 cm2 s−1. For BPSH 40, the diffusion coefficient dropped significantly over the same concentration range, from 7.7 × 10−6 to 2.5 × 10−6cm2 s−1. The difference in diffusion behavior is largely related to the amount of solvent sorbed by the membranes. Increasing the methanol concentration results in an increase in solvent uptake for Nafion 117, while BPSH 40 actually excludes the solvent at higher concentrations. In contrast, diffusion of methanol measured via permeability measurements (assuming a partition coefficient of 1) was lower (1.3 × 10−6 and 6.4 × 10−7 cm2 s−1 for Nafion 117 and BPSH 40 respectively) and showed no concentration dependence. The differences observed between the two techniques are related to the length scale over which diffusion is monitored and the partition coefficient, or solubility, of methanol in the membranes as a function of concentration. For the permeability measurements, this length is equal to the thickness of the membrane (178 and 132 μm for Nafion 117 and BPSH 40 respectively) whereas the NMR method observes diffusion over a length of approximately 4–8 μm. Regardless of the measurement technique, BPSH 40 is a greater barrier to methanol permeability at high methanol concentrations. 相似文献
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三维结构氧化石墨烯载铂催化剂对甲醇电催化性能 《燃料化学学报》2017,45(2):194-199
喷雾干燥法制备具有三维结构的氧化石墨烯(PGO),在其表面进一步负载活性成分Pt,得到纳米Pt/PGO复合催化剂。采用X射线粉末衍射(XRD)、透视电镜(TEM)和扫描电镜(SEM)等对催化剂的形貌和结构进行表征。结果表明,PGO具有类似于长4-6μm和宽2.0-3.0μm的三维纸团结构,平均粒径为4.2 nm的Pt纳米粒子均匀分布在其表面。采用循环伏安和计时电流法研究了在酸性溶液中催化剂对甲醇的电催化氧化性能。结果表明,Pt/PGO催化剂对甲醇呈现出更高的电催化氧化活性和稳定性。PGO所具有的三维结构和双功能作用机理有利于甲醇在铂表面的电催化氧化过程的发生。 相似文献
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1975年美国Chem Systems Inc公司提出液相法甲醇合成工艺的概念,采用导热性能优良的液体作为热载体,床层温度均匀易控,从而可提高原料气的单程转化率,出口甲醇质量分数可达到15%。传统浆态床反应器相对固定床虽然具有良好的传热性能,温度分布比较均匀,但是浆态床由于液体溶剂的存在以及气体分布不均匀,给传质过程带来了负面影响,增加了体系的复杂性。尽管优化气体分布器结构,可以起到改善传质的效果,但是还是无法明显改善传统浆态床内气液传质性能,反应器内固体沉积团聚严重。循环气流床通过循环泵的强制循环和喷嘴的雾化作用,相比如传统浆态床反应器,具有良好的传质能力、固体悬浮,并且能有效地减少轴向返混,具有相间接触充分、气液比(气固比)调节灵活、催化剂利用率高等特点。本实验研究了空速、循环量、喷嘴个数、催化剂浓度对甲醇合成的影响,为以后反应器的放大优化提供基础数据。 相似文献
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The transport of methanol through Nafion® membrane in diffusion cell is investigated using the open circuit potential method at different initial methanol concentration solutions. A simple mathematical model based on quasi-steady-state diffusion for the transport of methanol across the membrane in a diffusion cell is developed to simulate the experimental data in order to measure the methanol permeability. The influence of the diffusion cell parameters and thickness of the membrane on the methanol permeability measurement has been evaluated and analyzed. By means of Maclaurin expansion technique, this model can be used to predict the deviation of methanol permeability determined by steady-state diffusion model. 相似文献