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Electrochemical energy conversion in direct methanol fuel cells

机译:直接甲醇燃料电池中的电化学能量转换

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摘要

Direct methanol fuel cells (DMFCś) are promising candidates as portable power sources due to their lower weight, volume and high-energy density. They can potentially provide an energy content that exceeds current battery technology, with the possibility of instantaneous recharge. However, DMFCś have several serious drawbacks such as slow methanol oxidation kinetics, poisoning by CO of the catalyst surface, the high methanol crossover through the polymer membrane, the high costs of the Nafion membrane and catalyst. The flowing streams of fuel and oxidizer need to be evenly distributed over the entire surface of the catalyst layer in order to achieve a good performance together with an efficient removal of reaction products. This is achieved through the optimal design of the flow field. In this work the effect of flow field design on cell performance is studied, using polarization curves. A testing fuel cell was designed and implemented consisting of two stainless steel end plates, two sets of graphite collector plates, two carbon cloth diffusion layers, two catalyst layers of platinum black (0.70 mg.cm-2 and 0.75 mg.cm-2 Pt on cathode and anode, respectively) and an electrolyte polymer membrane (Nafion 117). Pt-Ru catalyst on the anode with a load of 4 mgcm-2 of catalyst was also studied. The active surface area of the cell is 25 cm2. An own built fuel cell and a Lyntech testing station were used in this work. The effects of temperature, methanol concentration, feeding flow rates of fuel and flow field design on the cell performance were studied. Results showed that the performance of the fuel cell increases with increase in cell temperature due to improvement in methanol oxidation kinetics and cathode kinetics, as indicated by polarization curves. The effect of temperature is complex; the oxygen partial pressure decreases with temperature increase due to the increase in vapor partial pressure, which causes decreases in the open-cell voltage and increases the concentration overpotential; the rate of methanol crossover increases with temperature, so the cell performance decreases; water transfer from anode to cathode through the membrane increases with temperature and the additional water increases the liquid water fraction in both the cathode catalyst and diffusion layers, thus causing an increase in concentration polarization. Increase in methanol concentration affected the performance of the DMFC, as expected due to a higher methanol crossover with higher concentrations. The methanol transferred from the anode to the cathode through the polymer electrolyte membrane is oxidized at the platinum electrocatalyst and causes a mixed potential, which lowers the cathode performance and thus the overall cell voltage output. The effect of the flow field design, single serpentine and parallel, on cell performance was also investigated. The serpentine flow field was better than the parallel design. The obtained results point towards an enhancement in the mass transfer of methanol improving the cell performance. Another important issue is the eventual blocking of the flow channels, by CO2, at high current densities. A reduction of the effective contact area between the fuel (methanol) and the gas diffusion layer is expected, as CO2 gas bubbles accumulate in the channels, bearing implications in the continuous supply of methanol to the catalyst sites through the gas diffusion layer. This is less likely to occur with the serpentine design. Cathode kinetics indicates slightly lower methanol crossover and better voltage efficiency at low current densities. Comparison is made with results obtained for the two different catalyst layers used emphasizing the effect of Ru.
机译:直接甲醇燃料电池(DMFCś)重量轻,体积小,能量密度高,因此有望成为便携式电源。它们可能会提供超出当前电池技术的能量含量,并且可能会即时充电。然而,DMFC具有若干严重的缺点,例如缓慢的甲醇氧化动力学,催化剂表面的CO所毒化,甲醇穿过聚合物膜的高穿越,Nafion膜和催化剂的高成本。燃料和氧化剂的流动流需要均匀地分布在催化剂层的整个表面上,以实现良好的性能以及有效地除去反应产物。这是通过对流场进行优化设计来实现的。在这项工作中,使用极化曲线研究了流场设计对电池性能的影响。设计并实施了一个测试燃料电池,它由两个不锈钢端板,两组石墨收集板,两个碳布扩散层,两个铂黑催化剂层(0.70 mg.cm-2和0.75 mg.cm-2 Pt)组成(分别在阴极和阳极上)和电解质聚合物膜(Nafion 117)。还研究了负载4 mgcm-2的阳极上的Pt-Ru催化剂。电池的有效表面积为25 cm2。这项工作使用了自己建造的燃料电池和Lyntech测试站。研究了温度,甲醇浓度,燃料进料流速和流场设计对电池性能的影响。结果表明,由于极化曲线表明,由于甲醇氧化动力学和阴极动力学的改善,燃料电池的性能随电池温度的升高而增加。温度的影响是复杂的。由于蒸气分压的增加,氧分压随温度的升高而降低,这导致开孔电压下降,浓度过电势增加。甲醇的穿越速率随温度增加而增加,因此电池性能下降;通过膜从阳极到阴极的水转移随温度增加,并且额外的水增加阴极催化剂和扩散层中的液态水分数,从而引起浓度极化增加。如预期的那样,甲醇浓度的增加影响了DMFC的性能,这是由于较高浓度下较高的甲醇穿透性。通过聚合物电解质膜从阳极转移到阴极的甲醇在铂电催化剂上被氧化并产生混合电位,这降低了阴极性能,从而降低了整个电池的电压输出。还研究了单蛇形和平行流场设计对电池性能的影响。蛇形流场比平行设计要好。所获得的结果表明甲醇传质的增强,从而改善了电池性能。另一个重要的问题是在高电流密度下最终会被CO2阻塞流道。由于CO 2气泡在通道中积聚,因此有望减少燃料(甲醇)与气体扩散层之间的有效接触面积,这意味着通过气体扩散层将甲醇连续供应至催化剂部位。蛇形设计不太可能发生这种情况。阴极动力学表明,在低电流密度下,甲醇的穿越率略低,电压效率更高。将获得的结果与使用两种不同催化剂层的结果进行比较,以强调Ru的作用。

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