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磁控溅射法制备YSZ电解质薄膜及其在SOFC中的应用

YSZ Electrolyte Films Fabricated by Magnetron Sputtering Technology and Its Application in Solid Oxide Fuel Cell

【作者】 柳志民

【导师】 孙克宁;

【作者基本信息】 哈尔滨工业大学 , 化学工程与技术, 2008, 硕士

【摘要】 固体氧化物燃料电池(SOFC)是一种全固态、高效的能量转换装置,由于自身特有的优点被认为是21世纪最有效的发电系统之一。目前研究的重点是开发可在中低温(600℃~800℃)区域工作的SOFC,为了保证电池良好的输出性能,Y2O3稳定的ZrO2(YSZ)电解质的薄膜化制备是一种非常有前景的技术路线。本文采用射频磁控溅射法制备YSZ电解质薄膜,研究了溅射过程中关键工艺参数对薄膜性能的影响。实验过程中主要通过对薄膜微观形貌、沉积速率以及组装单体电池性能的表征来优化工艺。确定的最佳工艺参数:沉积时间为35h,工作气压为0.75Pa,射频功率为350W,基体温度为600℃。采用优化后的溅射工艺获得的YSZ电解质薄膜再1400℃热处理2h,其厚度约为9μm,致密度高,与阳极基体结合紧密。组装单体电池,其开路电压可达到1.03V;电池在750℃、800℃和850℃时最大功率密度分别为570mW·cm-2、831m W·cm-2和1200mW·cm-2。另外研究了阳极基体对溅射制备YSZ电解质薄膜性能以及电池性能的影响。发现压片法制备的阳极预烧温度为1300℃时,片子的平整度和YSZ薄膜致密性较好,电池在800℃下的开路电压和最大功率密度分别为1.08V和834mW·cm-2;相对于压片法,采用流延法制备的阳极基体,颗粒分布均一,结构精细,催化活性高,电池的放电性能和稳定性较好,电池在800℃下的最大功率密度为1009mW·cm-2,运行10h基本无衰减。采用流延法烧制了70mm×70mm平整的NiO-YSZ阳极基体,在此基体上溅射了YSZ电解质薄膜,1400℃热处理2h后,薄膜的平整度和均匀性都较好,电解质致密度较高并且和电极结合紧密。

【Abstract】 Solid Oxide Fuel Cell (SOFC), which is a solid-state and high-energy efficiency conversion device, is considered as one of the most promising electricity generating devices in the 21th century because of its particular advantages. The key current research is the fabrication of SOFC operating at reduced temperature (600oC~800oC). For achieving predominant output of cell, reducing the thickness of YSZ electrolyte is a promising technology route.YSZ electrolyte film is fabricated by radio frequency magnetron sputtering technique. The influence of sputtering parameters on the performance of YSZ electrolyte film was studied. The technical parameters were optimized by the YSZ film morphology observation, the deposition rate and the performance of assembly fuel cells in the course of experiments. Deposition time for 35 h, Work pressure of 0.75 Pa, RF power of 350 W amd substrate temperature of 600℃are identified as the best technical parameters. Under these condtion, YSZ electrolyte film obtained by magnetron sputtering technology is quite dense after heat-treatment at 1400℃for 2h. The YSZ electrolyte film with a thickness of 9μm is well adhesive to the anode. The open circuit voltage (OCV) of the fuel cell with this YSZ film via sputtering technology is 1.03V at 800oC that is close to the theoretical voltage. The maximum power densities are 1200 mW·cm-2, 831mW·cm-2 and 570mW·cm-2 at 850°C, 800°C and 750°C, respectively.Furthermore, the influence of anode substrate on the performance of YSZ electrolyte film and fuel cell was studied. The anode substrate is prepared by dry-pressing method with pre-treatment tempreture of 1300oC, on which the sputtering YSZ electrolyte film reveals better smoothnesses and density. The OCV and the maximum power density were 1.08V and 834mW·cm-2, respectively. The function layer of anode prepared by tape-casting method has a fine structure, and the particle distribution of which is more homogeneous than that of anode obtained by dry-pressing method. The assembly cell with this anode behaves the better electrochemical performance and stability. The maximum power densities of this cell are 1009mW·cm-2 and no obviously decline is found during the test of 10h. Then, a piece of NiO-YSZ anode substrate with the sizes of 70mm×70mm was prepared by tape-casting method. The YSZ electrolyte film was sputtered on this substrate and heat-treaed at 1400℃for 2h. The smoothness and uniformity of YSZ electrolyte film is fine, and the YSZ electrolyte film was dense and well adhesive to the anode.

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