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随着全球能源结构转型的推进，固体氧化物燃料电池(SOFC)因其高效、清洁的能源转换特性成为研究热点。甲醇作为液态氢载体，具有储运安全、来源广泛等优势，其重整制氢耦合SOFC系统可规避氢气储运难题，提升能源利用效率。本工作针对甲醇蒸汽重整耦合平管型SOFC电堆系统，研究开发了一种基于吉布斯自由能最小化的平管型SOFC电堆模型，该模型执行热量和质量平衡，并在电压计算中考虑了欧姆、活化和浓度极化损失，可以预测不同运行条件下甲醇SOFC的发电特性，通过对比模拟计算结果与使用甲醇运行的平管型SOFC电堆实验数据验证了该模型的准确性。本工作还对电堆燃料利用率、电流密度和蒸汽与可燃碳(甲醇)的摩尔比等参数开展了敏感性分析，以深入了解主要变量对系统的影响。为甲醇SOFC系统的优化设计与稳定运行提供了理论与实验依据，对推动清洁能源高效利用具有重要意义。
Abstract：Introduction With the advancement of global energy transition,the development of efficient and clean energy conversion technologies becomes crucial to addressing energy shortages and environmental pollution.Solid oxide fuel cells(SOFCs) have attracted much attention due to their high energy conversion efficiency and fuel flexibility,while methanol as a liquid hydrogen carrier offers advantages such as safe storage/transportation and wide availability.However,a systematic research on the off-design performance and optimal design of methanol-SOFC systems remains insufficient,particularly for planar-tubular SOFC stacks through modeling and experimental validation.This study was to establish an accurate mathematical model combined with experimental verification to elucidate the power generation characteristics of methanol-SOFC systems under variable operating conditions,providing theoretical foundations and technical support for efficient and stable system operation.Methods This study proposed an equilibrium-based SOFC stack model based on the principle of minimizing Gibbs free energy,integrating heat and mass balance calculations,while comprehensively considering the effects of ohmic polarization,activation polarization,and concentration polarization on the voltage.An industrial-sized flat-tube SOFC stack(5 cells) was used to compare the power generation performance of pure hydrogen and methanol reforming gas at 750 ℃.The composition of the reforming gas was analyzed by gas chromatography,and the I-V curve was tested.A system flow model wss constructed using a software named Aspen Plus,and the I-V curves obtained from the SOFC system model simulation aligned closely with the experimental results,confirming the accuracy of the computational model used in this study.The sensitivity analysis was then performed to evaluate the effects of key parameters(i.e.,the steam-to-carbon molar ratio(STCR),fuel utilization rate(Uf),and current density) on the system performance.Results and discussion In the comparation of the performance of the SOFC system under pure hydrogen and methanol reforming gas power generation conditions,the maximum power density difference was only 5.59%,confirming the practicality of methanol fuel.Furthermore,the sensitivity analysis indicates that a) since anode carbon deposition is a key factor leading to stack failure,the impact of the steam-to-carbon molar ratio(STCR) on the system power generation performance is studied.The operating voltage decreases from 3.505 V to 3.226 V,and the system efficiency reduces from 45.95% to 42.35% when the STCR increases from 1 to 4(a commonly used STCR in industrial processes).A low STCR(=2) can balance both the efficiency and carbon deposition suppression;b) the impact of fuel utilization rate on the system power generation performance is investigated.The system efficiency increases from 35.79% to 57.25% when the fuel utilization rate increases from 55% to 95%.However,the excessive concentration polarization can be avoided,and a fuel utilization rate of 85% is recommended;and c) after determining the system's fuel utilization rate and STCR,the impact of current density on the system power generation performance is studied.The calculated current density range is 0.602-0.733 A·cm-2,with the operating voltage range of 3.25-3.50 V under the target power range conditions(i.e.,P=147.3-166.9 W).The system efficiency ranges from 38.18% to 43.27% at the optimal current density of 0.704 A·cm-2.Conclusions This study proposed a computational model for the methanol power generation characteristics of flat-tube SOFC stacks,enabling the performance prediction of the methanol-SOFC stack under different operating conditions.The accuracy of this model was validated through modeling and experimental results.The study further clarified the performance behavior of the methanol-SOFC system under varying conditions and proposed optimization ranges for key parameters.The results indicated that methanol fuel could effectively replace pure hydrogen,and the stack output power could be controlled under high voltage conditions.The efficient and stable operation could be achieved via adjusting the steam-to-carbon molar ratio,fuel utilization rate and current density.At an output power of 150 W,the optimal operating parameters were a steam-to-carbon molar ratio of 2,a fuel utilization rate of 85%,and a current density of 0.704 A·cm-2.Under the optimum conditions,the stack efficiency was 36.71%,and the system efficiency was 42.21%.The research findings could provide an important reference for the engineering application of methanol-SOFC systems and have significant implications for advancing clean energy technologies.
[1] ATILHAN S, PARK S, EL-HALWAGI M M, et al. Green hydrogen as an alternative fuel for the shipping industry[J]. Curr Opin Chem Eng,2021, 31:100668.
[2] YADAV M, XU Q. Liquid-phase chemical hydrogen storage materials[J]. Energy Environ Sci, 2012, 5(12):9698–9725.
[3] GONG C Y, XU Y H, CAI S S, et al. Comparative study on thermodynamic analysis of solid oxide fuel cells supplied with methanol or ammonia[J]. Int J Hydrog Energy, 2024, 50:1293–1301.
[4] BUONOMANO A, CALISE F, D’ACCADIA M D, et al. Hybrid solid oxide fuel cells–gas turbine systems for combined heat and power:A review[J]. Appl Energy, 2015, 156:32–85.
[5] ZHAO H B, HOU Q L. Thermodynamic performance study of the MR SOFC–HAT–CCHP system[J]. Int J Hydrog Energy, 2019, 44(8):4332–4349.
[6] TAPIERO D, TZABAR N, TARTAKOVSKY L. Performance of solid-oxide fuel cells operating with different sustainable fuel reformates[J]. J Power Sources, 2024, 611:234761.
[7] XU Q D, XIA L C, HE Q J, et al. Thermo–electrochemical modelling of high temperature methanol-fuelled solid oxide fuel cells[J]. Appl Energy, 2021, 291:116832.
[8] MENG T, CUI D A, JI Y L, et al. Optimization and efficiency analysis of methanol SOFC–PEMFC hybrid system[J]. Int J Hydrog Energy,2022, 47(64):27690–27702.
[9] RESEARCH Prof Phan Anh Duong Ph D, BO RIM RYU P D, TRAN THE NAM P D, et al. Comparative study of thermodynamic performances:Ammonia vs. methanol SOFC for marine vessels[J].Chem Eng Technol, 2024, 47(9):e202400118.
[10] YAO S G, YAN X, XIA M J, et al. Thermodynamic and economic analysis, optimization of SOFC/GT/SCO2/ORC hybrid power systems for methanol reforming-powered ships with carbon capture[J]. Case Stud Therm Eng, 2025, 67:105840.
[11] TAWEEKAYUJAN S, PRASERTCHAROENSUK P, CHEN Y S, et al.Enhancing methanol-to-power:A comprehensive evaluation of an integrated methanol-reforming, high-temperature proton exchange membrane fuel cell, and organic Rankine cycle system[J]. Energy, 2025,321:135301.
[12] YUAN S K, LI P J, JIAO F, et al. An efficient integrated system for methanol steam reforming to produce hydrogen coupled with PEMFC power generation[J]. J Therm Sci, 2025, 34(2):374–388.
[13] SANG J K, LIU S, YANG J, et al. Power generation from flat-tube solid oxide fuel cells by direct internal dry reforming of methanol:A route for simultaneous utilization of CO2 and biofuels[J]. Chem Eng J,2023, 457:141189.
[14] LIU Z, WANG C T, HAN B B, et al. Flat-tube solid oxide stack with high performance for power generation and hydrogen production[J].Appl Energy, 2024, 362:122999.
[15] WANG J P, ZHAO Y M, YANG J, et al. Understanding thermal and redox cycling behaviors of flat-tube solid oxide fuel cells[J]. Int J Hydrog Energy, 2023, 48(57):21886–21897.
[16] COSTAMAGNA P, MAGISTRI L, MASSARDO A F. Design and part-load performance of a hybrid system based on a solid oxide fuel cell reactor and a micro gas turbine[J]. J Power Sources, 2001, 96(2):352–368.
[17] HOFMANN P, PANOPOULOS K D, FRYDA L E, et al. Comparison between two methane reforming models applied to a quasi-twodimensional planar solid oxide fuel cell model[J]. Energy, 2009, 34(12):2151–2157.
[18] PANOPOULOS K D, FRYDA L E, KARL J, et al. High temperature solid oxide fuel cell integrated with novel allothermal biomass gasification Part I:Modelling and feasibility study[J]. J Power Sources,2006, 159(1):570–585.
[19] ZHANG W, CROISET E, DOUGLAS P L, et al. Simulation of a tubular solid oxide fuel cell stack using AspenPlusTM unit operation models[J]. Energy Convers Manag, 2005, 46(2):181–196.
[20] SUWANWARANGKUL R, CROISET E, PRITZKER M D, et al.Modelling of a cathode-supported tubular solid oxide fuel cell operating with biomass-derived synthesis gas[J]. J Power Sources, 2007, 166(2):386–399.
[21] CAMPANARI S, IORA P. Definition and sensitivity analysis of a finite volume SOFC model for a tubular cell geometry[J]. J Power Sources,2004, 132(1/2):113–126.
[22] HUSSAIN J, ALI R, AKHTAR M N, et al. Modeling and simulation of planar SOFC to study the electrochemical properties[J]. Curr Appl Phys,2020, 20(5):660–672.
[23] TAPIERO D, DISKIN D, TZABAR N, et al. Performance of solid-oxide fuel cells fed with pure hydrogen and methanol steam reforming products–experimental study[J]. Int J Hydrog Energy, 2024,50:1427–1440.
[24] AGUIAR P, ADJIMAN C S, BRANDON N P. Anode-supported intermediate temperature direct internal reforming solid oxide fuel cell.I:Model-based steady-state performance[J]. J Power Sources, 2004,138(1/2):120–136.
[25] BRAUN R J. Optimal design and operation of solid oxide fuel cell systems for small-scale stationary applications[D]. Madison, WI, USA:The University of Wisconsin-Madison, 2002.
[26] SEZER S, KARTAL F, U?UR?. Artificial intelligence approach in gasification integrated solid oxide fuel cell cycle[J]. Fuel, 2022, 311:122591.
[27] BAE Y, LEE S, YOON K J, et al. Three-dimensional dynamic modeling and transport analysis of solid oxide fuel cells under electrical load change[J]. Energy Convers Manag, 2018, 165:405–418.
[28] LISBONA P, CORRADETTI A, BOVE R, et al. Analysis of a solid oxide fuel cell system for combined heat and power applications under non-nominal conditions[J]. Electrochim Acta, 2007, 53(4):1920–1930.
[29] LEE T S, CHUNG J N, CHEN Y C. Design and optimization of a combined fuel reforming and solid oxide fuel cell system with anode off-gas recycling[J]. Energy Convers Manag, 2011, 52(10):3214–3226.
[30] TANIM T, BAYLESS D J, TREMBLY J P. Modeling a 5 k We planar solid oxide fuel cell based system operating on JP-8 fuel and a comparison with tubular cell based system for auxiliary and mobile power applications[J]. J Power Sources, 2014, 245:986–997.
[31] DOHERTY W, REYNOLDS A, KENNEDY D. Computer simulation of a biomass gasification-solid oxide fuel cell power system using Aspen Plus[J]. Energy, 2010, 35(12):4545–4555.
[32] SANTIN M, TRAVERSO A, MAGISTRI L, et al. Thermoeconomic analysis of SOFC–GT hybrid systems fed by liquid fuels[J]. Energy,2010, 35(2):1077–1083.
[33] CALISE F, DENTICE D’ACCADIA M, PALOMBO A, et al.Simulation and exergy analysis of a hybrid solid oxide fuel cell(SOFC)–gas turbine system[J]. Energy, 2006, 31(15):3278–3299.
[34] WANG Y G, LI H Y, LYU Z W, et al. Study of operating conditions for high efficiency and anode safety of industrial-size solid oxide fuel cell[J]. Acta Chim Sin, 2022, 80(8):1091.
[35] AMERI M, MOHAMMADI R. Simulation of an atmospheric SOFC and gas turbine hybrid system using Aspen Plus software[J]. Int J Energy Res, 2013, 37(5):412–425.
[36] COCCO D, TOLA V. Externally reformed solid oxide fuel cell–microgas turbine(SOFC–MGT)hybrid systems fueled by methanol and di-methyl-ether(DME)[J]. Energy, 2009, 34(12):2124–2130.
基本信息:
DOI：10.14062/j.issn.0454-5648.20250099
中图分类号:TM911.4
引用信息:
[1]王紫寒,杨钧,桑君康,等.甲醇固体氧化物燃料电池平管型电堆与系统的变工况性能模拟[J].硅酸盐学报,2025,53(10):2963-2972.DOI:10.14062/j.issn.0454-5648.20250099.
基金信息:
国家重点研发计划（2021YFB2500402）
2025-10-14
2025-10-14