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CH4/CO2直接內重整環境下平管型SOFC電堆的穩定性

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

  • 摘要: 構建了一個由三片平管型固體氧化物電池組成的電池堆,并對氫氣和CH4/CO2干重整條件下的電堆發電特性進行了對比分析,探究了CH4/CO2比例和電流密度對電堆瞬時和長期催化重整性能的影響,并分別監測了每片電池的性能變化. 結果顯示:在750 °C時,使用氫氣為燃料與干重整氣為燃料的最大放電功率分別為100.0 W與81.1 W,電池堆的非電池部分功率消耗分別為17.6 W和9.8 W. 在15 A的恒電流測試中,氫氣環境下電池堆在100 h后電壓衰減率為0.0130%·h?1;而在CO2/CH4條件下,電池堆在360 h后電壓增長率為0.0096%·h?1. 長期運行中,遠離燃料入口的第三片電池是電池堆性能衰減的主要因素. 模擬仿真結果表明,隨著電池離進氣口距離增加,氣體流速和含量因流道阻力和擴散效應而逐漸降低. 這些發現證實了平管型電池在甲烷干重整過程中具有出色的穩定性,體現出其潛在優勢與可靠性.

     

    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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