固体氧化物燃料电池的激光增材制造工艺开发

固体氧化物燃料电池（Solid Oxide Fuel Cells，SOFCs）是一种具有清洁高效优势的新能源装置，但SOFC传统的制造工艺存在局限，例如：较大厚度和复杂结构的SOFC难以制备，后组装也无法摆脱繁琐的密封过程，共烧结工艺参数难以摸索等，因此开发一种新型的可对SOFC进行加工制造的工艺有很大的必要性。本论文旨在使用激光增材制造技术中的选区激光熔化（Selective Laser Melting，SLM）技术来对SOFC进行工艺开发。

本论文对Ni-Fe金属支撑层的SLM成型工艺、微观组织与相组成进行了研究。结果表明SLM技术适用于块体Ni-Fe的成型，并且成型的样品致密度最高达到了99.8%。SLM成型的Ni-Fe支撑体元素分布均匀，没有出现相的转变和新相的生成。另外SLM成型的Ni-Fe存在一定的择优取向，其晶粒平均尺寸为90 μm。又对基于Ni-Fe+CrN粉末体系的多孔金属支撑层进行了SLM工艺探索。在引入发泡剂CrN后，试样的孔隙特征达到了SOFC金属支撑层的要求，其对应的能量密度集中在35 J/mm³~50 J/mm³范围。

论文还对氧化钇稳定氧化锆（Yttria Stabilized Zirconia，YSZ）电解质层、Ni-YSZ阳极功能层、镧锶钴铁（La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ，LSCF）阴极层进行了打印成型参数探索，确定了只有在低功率、小扫描速度、大搭接间距的参数下才能实现符合要求的Ni-YSZ、YSZ、LSCF的打印成型。其中符合SOFC阳极功能层（孔隙率30%~40%）的打印参数为能量密度30 J/mm³。符合SOFC致密态电解质层的打印参数为激光功率80 W、扫描速度83 mm/s、搭接间距0.2 mm。符合SOFC阴极层（孔隙率30%~40%）的打印参数为激光功率60 W、扫描速度200 mm/s、搭接间距0.2 mm。 

论文在单层材料打印参数基础上，最后对电池进行了全打印研究。发现其Ni-YSZ、YSZ、LSCF离焦量参数为+4 mm时，可以实现目标厚度的打印。并且对全打印的SOFC进行电池性能测试，虽然发现其开路电压（0.02 V）低于理论开路电压（1.23 V），但是论文证明了激光增材制造技术有制造出SOFC的潜力。

Solid oxide fuel cells (SOFCs) are new energy devices with clean and efficient advantages. However, the traditional manufacturing process of SOFC often has limitations. For example, SOFC with large thickness and complex structure is difficult to prepare, and post-assembly cannot get rid of the tedious sealing process, and it is difficult to explore the co-sintering process parameters. Therefore, it is very necessary to develop a new process that can process SOFC. This thesis aims at process development of SOFC using Selective Laser Melting (SLM) technology in laser additive manufacturing.

In this dissertation, the SLM forming process, microstructure and phase composition of Ni-Fe metal support were studied. The results show that the SLM technology is suitable for the forming of Ni-Fe, and the density of the formed samples is up to 99.8%. The element distribution of the Ni-Fe support formed by SLM is uniform, and there is no phase transition and no new phase formation. In addition, the Ni-Fe formed by SLM has a certain preferred orientation, and the average grain size is 90 μm. Then, the SLM process was also explored for the porous metal support layer based on Ni-Fe+CrN powder system. After introducing the foaming agent CrN, the pore characteristics of the samples meet the requirements of the SOFC metal support layer, and the corresponding energy densities are concentrated in the range of 35 J/mm³~50 J/mm³.

The dissertation also explores the printing parameters of the YSZ electrolyte layer, Ni-YSZ anode functional layer, and LSCF cathode layer. It is determined that only under the parameters of low power, small scanning speed, and large hatch spacing can meet the requirements of Ni-YSZ, YSZ, LSCF printing. Among them, the printing parameters in line with the SOFC anode functional layer (porosity 30%~40%) are the energy density of 30 J/mm³. The printing parameters conforming to the SOFC dense electrolyte layer are the laser power of 80 W, the scanning speed of 83 mm/s, and the hatch spacing of 0.2 mm. The printing parameters suitable for the SOFC cathode layer (porosity 30%~40%) are laser power 60 W, scanning speed 200 mm/s, and hatch spacing 0.2 mm.

Based on the printing parameters of the single-layer material, the dissertation finally studies the full printing of the battery. It is found that the printing of the target thickness can be achieved when the defocus parameters of Ni-YSZ, YSZ and LSCF are +4 mm. The battery performance test was carried out on the fully printed SOFC, Its open circuit voltage (0.02 V) was found to be lower than the theoretical open circuit voltage (1.23 V), but the dissertation demonstrates that laser additive manufacturing has the potential to manufacture SOFCs.

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