CH4/CO2直接内重整环境下平管型SOFC电堆的稳定性

Stability of flat tube SOFC stack with CH4/CO2 direct internal reforming

  • 摘要: 构建了一个由三片平管型固体氧化物电池组成的电池堆,并对氢气和CH4/CO2干重整条件下的电堆发电特性进行了对比分析,探究了CH4/CO2比例和电流密度对电堆瞬时和长期催化重整性能的影响,并分别监测了每片电池的性能变化. 结果显示:在750 °C时,使用氢气为燃料与干重整气为燃料的最大放电功率分别为100.0 W与81.1 W,电池堆的非电池部分功率消耗分别为17.6 W和9.8 W. 在15 A的恒电流测试中,氢气环境下电池堆在100 h后电压衰减率为0.0130%·h−1;而在CO2/CH4条件下,电池堆在360 h后电压增长率为0.0096%·h−1. 长期运行中,远离燃料入口的第三片电池是电池堆性能衰减的主要因素. 模拟仿真结果表明,随着电池离进气口距离增加,气体流速和含量因流道阻力和扩散效应而逐渐降低. 这些发现证实了平管型电池在甲烷干重整过程中具有出色的稳定性,体现出其潜在优势与可靠性.

     

    Abstract: Solid oxide fuel cells (SOFCs) are highly efficient and eco-friendly energy conversion devices that can utilize hydrocarbon fuels such as natural gas and biogas. However, the commonly used yttria-stabilized zirconia (Ni-YSZ) anode materials are prone to carbon deposition, which can block the porous structure of the anode and lead to the degradation of cell performance and even cell failure. A dry reforming strategy using CO2 for CH4 reforming can shift the CH4 fuel from coking to non-coking zones, thereby eliminating the possibility of carbon deposition from a thermodynamic perspective. This approach not only simplifies the system and reduces power generation costs, but also enables the reuse of CO2. The reforming reaction is endothermic and can significantly affect the internal thermal field distribution within the cell. Traditional planar cells, which have an axisymmetric design, can develop localized thermal stresses on one side during CH4 reformation at the anode, potentially causing cell warping or cracking. To address this issue, a thick anode support with a through-hole structure can be used as a catalytic layer. This modification enhances cell symmetry, creating a quasi-centrosymmetric flat-tube SOFC that allows for an isotropic distribution of thermal stresses and significantly reduces the risk of cell warping or fracture. In this study, a stack of three flat-tube SOFCs was constructed, and the power-generation characteristics of the stack under hydrogen and CH4/CO2 dry reforming conditions were compared. In addition, the performance changes in each cell were monitored. As per the results, the maximum power output of the three-cell stack at 750 °C on using hydrogen and dry reforming gas as fuels were 100.0 and 81.1 W, respectively, with power consumptions of the non-cell parts of the stack being 17.6 and 9.8 W, respectively. IV curves indicated that at a CO2/CH4 flow of 1.2 L·min−1/0.6 L·min−1, the stack’s dry reforming performance approached its limit, making significant increases in output power unlikely with higher CO2 content. At a 1∶1 CO2/CH4 feed ratio, the tail gas measurements indicated a fuel utilization rate of 55.8% at 18 A. During a constant current test at 15 A, after 100 h in a hydrogen environment, the stack voltage degradation rate was 0.130‰·h−1. The interfacial resistance increasing from an initial 11.1 mΩ to 17.5 mΩ (growth rate: ~0.554%·h−1), which is much higher than that of the stack. This indicates that stack degradation was primarily due to the increase in interfacial resistance rather than a decline in the single-cell performance. Under CO2/CH4 conditions, after 360 h of operation, the stack voltage growth rate was 0.0096%·h−1, with the interfacial resistance stabilizing at ~31 mΩ (growth rate: ~0.0183%·h−1). This further supports the excellent dry-reforming performance of the stack. Long-term operation suggested possible fuel starvation in Cell-3 (the cell farthest from the fuel inlet), which caused partial oxidation and reduced the catalytic activity. This was inferred to be the main factor in stack performance degradation. Simulation results confirmed that as the gas passes through the stack, the gas flow velocity and content decrease in subsequent cells owing to the flow channel resistance and diffusion effects. These findings demonstrate that the degradation range of the flat-tube stack under CH4/CO2 dry reforming is relatively small. This indicates that the flat-tube stack exhibits relatively stable methane dry reforming performance, reflecting its potential advantages and reliability in CH4/CO2 dry reforming applications.

     

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