基于组合参数分析的质子交换膜燃料电池性能优化数值研究
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摘要
质子交换膜燃料电池(PEMFC)由于不受卡诺循环限制、能量转化率高、可室温快速启动、无电解液流失、水易排除、寿命长、比功率与比能量高等突出优点,是目前最有希望应用于便携式电源、小型固定发电站、电动汽车等交通工具的动力电源。但是PEMFC目前还处于研究阶段,它的一些机理和关键问题还没有解决。质子交换膜燃料电池多参数同时变化对电池性能的影响以及电池极化曲线为什么重合就是其中还没有解决的两个关键问题。
本文首先采用Gambit2.2建立了一个平行流场PEMFC几何模型,通过计算流体力学软件Fluent6.3建立三维、两相、非等温、稳态数学模型,其中描述了PEMFC流动、传热与传质、电化学反应和水传递等模型。
其次,本文采用正交设计、模糊熵权法与数值模拟相结合,系统研究了12个参数同时变化对电池极化曲线的影响以及参数间的交互关系。结果表明:阴极传递系数、阴极交换电流密度、氧气参考浓度、氧气在参考状态下的扩散系数对电池极化曲线有高度显著影响;阳极交换电流密度、扩散层的绝对渗透率对电池极化曲线有显著影响;扩散层孔隙率、氢气在参考状态下的扩散系数、水在参考状态下的扩散系数对电池极化曲线有一定影响;阳极传递系数、氢气参考浓度对电池极化曲线影响比较小。阴极传递系数与氧气在参考状态下的扩散系数、阴极交换电流密度与氧气参考浓度、阴极交换电流密度与氧气在参考状态下的扩散系数、氧气参考浓度与氧气在参考状态下的扩散系数有高度显著的交互作用;阴极传递系数与阴极交换电流密度、阴极传递系数与氧气参考浓度有显著的交互作用;阴极传递系数与阴极交换电流密度及氧气在参考状态下的扩散系数有一定的交互作用;其余的参数间的交互作用比较小。
最后,在上述研究的基础上,根据电化学关联式,重点对影响电池极化曲线较大的3个高敏感参数及另外3个对电池极化曲线影响略大的敏感参数进行了研究,探寻他们在什么情况下才能使极化曲线重合,以及他们与极化曲线重合的内在关系。研究结果表明:当保持PEMFC其他参数不变时,在参数取值区间内,同时改变阳极交换电流密度和氢气参考浓度,并使其满足特定关系式时,极化曲线完全重合;当保持PEMFC其他参数不变时,在参数取值区间内,同时改变阴极交换电流密度和氧气参考浓度,并使其满足特定关系式时,极化曲线完全重合;当保持PEMFC其他参数不变时,在参数取值区间内,同时改变阳极交换电流密度和阳极传递系数,并使其满足特定关系式时,极化曲线完全重合;当保持PEMFC其他参数不变时,在参数取值区间内,同时改变阴极交换电流密度和阴极传递系数,不能使极化曲线完全重合,但改变这两个参数可能会出现极化曲线部分重合;当保持PEMFC其他参数不变时,在参数取值区间内,同时改变阳极交换电流密度与阴极交换电流密度或者阳极传递系数与阴极传递系数,不能使极化曲线完全重合,但可能出现极化曲线部分重合;当保持PEMFC其他参数不变时,在参数取值区间内,同时改变阳极交换电流密度、氢气参考浓度、阳极传递系数,使其满足某些特定关系式时,极化曲线完全重合;当保持PEMFC其他参数不变时,在参数取值区间内,同时改变阴极交换电流密度、氧气参考浓度、阴极传递系数,不能使极化曲线完全重合。但其有可能使极化曲线近似重合;当保持PEMFC其他参数不变时,在参数取值区间内,同时改变阳极交换电流密度、氢气参考浓度、阴极交换电流密度、氧气参考浓度,使其满足某些特定关系式时,极化曲线不重合。但是当加上某些约束条件,极化曲线完全重合。
PEMFC的性能受诸多参数的影响,对参数组合的研究,不仅减少了参数的研究个数,更重要的是一种全新研究方法在PEMFC性能优化研究方面的应用,促进了PEMFC基础理论研究的发展:通过分析参数之间的相互关系,揭示电池性能控制的微观机理,避免了单一参数研究的不足之处;通过分析组合参数的物理意义,为深入研究打下基础;通过分析组合参数或约束条件与极化曲线之间的关系,明确电池性能优化的方向。
Proton exchange membrane fuel cell (PEMFC) has became the most promising applications of portable power, small-scale stationary power plants, electric vehicles and other modes of transport power supply ,because its not only have high-energy efficiency, quick start at room temperature, no electrolyte loss, long life, easy to water exclude, but also not subject to Carnot cycle limit. But the actual PEMFC is still in the researching stage, and some of critical questions aren’t dissolved. The polarization coincide is one of them, so this paper aims at researching polarization coincide of PEMFC.
First in this paper, a parallel flow field PEMFC geometrical model was developed by Gambit2.2, and at the same time, developing a three-dimensional, non-isothermal, steady mathematic model of PEMFC by Fluent6.3. And it describe fluid flow model, mass and heat transfer model, electrochemistry reaction model, water transfer model and so on.
Second, combined with orthogonal design, fuzzy entropy weight method and numerical simulation, systematic study the impacting of PEMFC polarization and interactions among the 12 parameters. The results show that: cathode transfer coefficient, cathode exchange current density, oxygen reference concentration, reference diffusion coefficient of oxygen are main affecting factors to the battery polarization; anode exchange current density, diffusion layer absolute permeability have significant influence to the cell polarization; Diffusion layer porosity , hydrogen diffusion coefficient in the reference state , water diffusion coefficient in the reference state have certain influence to the cell polarization; anode transfer coefficient, hydrogen concentration have relatively small impact to the cell polarization. cathode transfer coefficient and reference diffusion coefficient of oxygen, cathode exchange current density and oxygen reference concentration, cathode exchange current density and reference diffusion coefficient of oxygen, oxygen reference concentration and reference diffusion coefficient of oxygen have almighty significant interactions; cathode transfer coefficient and the cathode exchange current density, cathode transfer coefficient and the oxygen reference concentration have significant interaction; cathode transfer coefficient and the cathode exchange current density and oxygen diffusion coefficient in the reference state have certain interaction; the rest of other parameters have relatively small interaction.
Final,based on previous studies, according to electrochemical correlation, emphasis research three highly sensitive parameters and three sensitive parameters, try to find polarization curves coincide, and the intrinsic relationship between parameters and polarization coincide. The results show that:(1)under the condition of keeping PEMFC other parameters unchanged, in the parameter value ranges, change the anode reference exchange current density and the concentration of hydrogen, and make it contented specific relationship, polarization curves completely coincide;(2) under the condition of keeping PEMFC other parameters unchanged, in the parameter value ranges, change the cathode reference exchange current density and oxygen concentration, and make it contented specific relationship, polarization curves completely coincide;(3) under the condition of keeping PEMFC other parameters unchanged, in the parameter value ranges, change the anode exchange current density and anode transfer coefficient, and make it contented specific relationship, polarization curves completely coincide;(4) under the condition of keeping PEMFC other parameters unchanged, in the parameter value ranges, change the cathode exchange current density and cathode transfer coefficient, polarization curve can not coincide. But changes the two parameters may make polarization curves piece overlap;(5) under the condition of keeping PEMFC other parameters unchanged, in the parameter value ranges, change the anode exchange current density and cathode exchange current density or anode transfer coefficient and the cathode transfer coefficient, and make it contented specific relationship, the polarization curve can not coincide, but the polarization curves may piece overlap;(6) under the condition of keeping PEMFC other parameters unchanged, in the parameter value ranges, change the anode exchange current density, hydrogen reference concentration, anode transfer coefficient, and make it contented specific relationship, polarization curves completely coincide;(7) under the condition of keeping PEMFC other parameters unchanged, in the parameter value ranges, change the cathode exchange current density, oxygen reference concentration, cathode transfer coefficient, the polarization curve can not coincide. But polarization maybe partly coincide;(8) under the condition of keeping PEMFC other parameters unchanged, in the parameter value ranges, change the anode exchange current density, hydrogen reference to the concentration of the cathode exchange current density, oxygen concentration reference, and make it contented specific relationship, polarization curve can not coincide. But when combined with certain constraints, polarization curves completely coincide.
PEMFC performance is influenced by many parameters, the research of combination parameters, not only reduced the parameter research integer, but more importantly is that one brand-new research technique is applicated in PEMFC performance optimization research, and promoted the PEMFC basic study development. Through analyzes the parameters reciprocity, it could revelation the control microscopic mechanism of battery, avoiding the sole parameter research deficiency. Through analysis the combination parameter's physics significance, it could build the foundation for deep research. Through analysis the combination parameter or the constraints and polarization curve's relations, it would give us clear direction about the battery performance optimizes.
本文首先采用Gambit2.2建立了一个平行流场PEMFC几何模型,通过计算流体力学软件Fluent6.3建立三维、两相、非等温、稳态数学模型,其中描述了PEMFC流动、传热与传质、电化学反应和水传递等模型。
其次,本文采用正交设计、模糊熵权法与数值模拟相结合,系统研究了12个参数同时变化对电池极化曲线的影响以及参数间的交互关系。结果表明:阴极传递系数、阴极交换电流密度、氧气参考浓度、氧气在参考状态下的扩散系数对电池极化曲线有高度显著影响;阳极交换电流密度、扩散层的绝对渗透率对电池极化曲线有显著影响;扩散层孔隙率、氢气在参考状态下的扩散系数、水在参考状态下的扩散系数对电池极化曲线有一定影响;阳极传递系数、氢气参考浓度对电池极化曲线影响比较小。阴极传递系数与氧气在参考状态下的扩散系数、阴极交换电流密度与氧气参考浓度、阴极交换电流密度与氧气在参考状态下的扩散系数、氧气参考浓度与氧气在参考状态下的扩散系数有高度显著的交互作用;阴极传递系数与阴极交换电流密度、阴极传递系数与氧气参考浓度有显著的交互作用;阴极传递系数与阴极交换电流密度及氧气在参考状态下的扩散系数有一定的交互作用;其余的参数间的交互作用比较小。
最后,在上述研究的基础上,根据电化学关联式,重点对影响电池极化曲线较大的3个高敏感参数及另外3个对电池极化曲线影响略大的敏感参数进行了研究,探寻他们在什么情况下才能使极化曲线重合,以及他们与极化曲线重合的内在关系。研究结果表明:当保持PEMFC其他参数不变时,在参数取值区间内,同时改变阳极交换电流密度和氢气参考浓度,并使其满足特定关系式时,极化曲线完全重合;当保持PEMFC其他参数不变时,在参数取值区间内,同时改变阴极交换电流密度和氧气参考浓度,并使其满足特定关系式时,极化曲线完全重合;当保持PEMFC其他参数不变时,在参数取值区间内,同时改变阳极交换电流密度和阳极传递系数,并使其满足特定关系式时,极化曲线完全重合;当保持PEMFC其他参数不变时,在参数取值区间内,同时改变阴极交换电流密度和阴极传递系数,不能使极化曲线完全重合,但改变这两个参数可能会出现极化曲线部分重合;当保持PEMFC其他参数不变时,在参数取值区间内,同时改变阳极交换电流密度与阴极交换电流密度或者阳极传递系数与阴极传递系数,不能使极化曲线完全重合,但可能出现极化曲线部分重合;当保持PEMFC其他参数不变时,在参数取值区间内,同时改变阳极交换电流密度、氢气参考浓度、阳极传递系数,使其满足某些特定关系式时,极化曲线完全重合;当保持PEMFC其他参数不变时,在参数取值区间内,同时改变阴极交换电流密度、氧气参考浓度、阴极传递系数,不能使极化曲线完全重合。但其有可能使极化曲线近似重合;当保持PEMFC其他参数不变时,在参数取值区间内,同时改变阳极交换电流密度、氢气参考浓度、阴极交换电流密度、氧气参考浓度,使其满足某些特定关系式时,极化曲线不重合。但是当加上某些约束条件,极化曲线完全重合。
PEMFC的性能受诸多参数的影响,对参数组合的研究,不仅减少了参数的研究个数,更重要的是一种全新研究方法在PEMFC性能优化研究方面的应用,促进了PEMFC基础理论研究的发展:通过分析参数之间的相互关系,揭示电池性能控制的微观机理,避免了单一参数研究的不足之处;通过分析组合参数的物理意义,为深入研究打下基础;通过分析组合参数或约束条件与极化曲线之间的关系,明确电池性能优化的方向。
Proton exchange membrane fuel cell (PEMFC) has became the most promising applications of portable power, small-scale stationary power plants, electric vehicles and other modes of transport power supply ,because its not only have high-energy efficiency, quick start at room temperature, no electrolyte loss, long life, easy to water exclude, but also not subject to Carnot cycle limit. But the actual PEMFC is still in the researching stage, and some of critical questions aren’t dissolved. The polarization coincide is one of them, so this paper aims at researching polarization coincide of PEMFC.
First in this paper, a parallel flow field PEMFC geometrical model was developed by Gambit2.2, and at the same time, developing a three-dimensional, non-isothermal, steady mathematic model of PEMFC by Fluent6.3. And it describe fluid flow model, mass and heat transfer model, electrochemistry reaction model, water transfer model and so on.
Second, combined with orthogonal design, fuzzy entropy weight method and numerical simulation, systematic study the impacting of PEMFC polarization and interactions among the 12 parameters. The results show that: cathode transfer coefficient, cathode exchange current density, oxygen reference concentration, reference diffusion coefficient of oxygen are main affecting factors to the battery polarization; anode exchange current density, diffusion layer absolute permeability have significant influence to the cell polarization; Diffusion layer porosity , hydrogen diffusion coefficient in the reference state , water diffusion coefficient in the reference state have certain influence to the cell polarization; anode transfer coefficient, hydrogen concentration have relatively small impact to the cell polarization. cathode transfer coefficient and reference diffusion coefficient of oxygen, cathode exchange current density and oxygen reference concentration, cathode exchange current density and reference diffusion coefficient of oxygen, oxygen reference concentration and reference diffusion coefficient of oxygen have almighty significant interactions; cathode transfer coefficient and the cathode exchange current density, cathode transfer coefficient and the oxygen reference concentration have significant interaction; cathode transfer coefficient and the cathode exchange current density and oxygen diffusion coefficient in the reference state have certain interaction; the rest of other parameters have relatively small interaction.
Final,based on previous studies, according to electrochemical correlation, emphasis research three highly sensitive parameters and three sensitive parameters, try to find polarization curves coincide, and the intrinsic relationship between parameters and polarization coincide. The results show that:(1)under the condition of keeping PEMFC other parameters unchanged, in the parameter value ranges, change the anode reference exchange current density and the concentration of hydrogen, and make it contented specific relationship, polarization curves completely coincide;(2) under the condition of keeping PEMFC other parameters unchanged, in the parameter value ranges, change the cathode reference exchange current density and oxygen concentration, and make it contented specific relationship, polarization curves completely coincide;(3) under the condition of keeping PEMFC other parameters unchanged, in the parameter value ranges, change the anode exchange current density and anode transfer coefficient, and make it contented specific relationship, polarization curves completely coincide;(4) under the condition of keeping PEMFC other parameters unchanged, in the parameter value ranges, change the cathode exchange current density and cathode transfer coefficient, polarization curve can not coincide. But changes the two parameters may make polarization curves piece overlap;(5) under the condition of keeping PEMFC other parameters unchanged, in the parameter value ranges, change the anode exchange current density and cathode exchange current density or anode transfer coefficient and the cathode transfer coefficient, and make it contented specific relationship, the polarization curve can not coincide, but the polarization curves may piece overlap;(6) under the condition of keeping PEMFC other parameters unchanged, in the parameter value ranges, change the anode exchange current density, hydrogen reference concentration, anode transfer coefficient, and make it contented specific relationship, polarization curves completely coincide;(7) under the condition of keeping PEMFC other parameters unchanged, in the parameter value ranges, change the cathode exchange current density, oxygen reference concentration, cathode transfer coefficient, the polarization curve can not coincide. But polarization maybe partly coincide;(8) under the condition of keeping PEMFC other parameters unchanged, in the parameter value ranges, change the anode exchange current density, hydrogen reference to the concentration of the cathode exchange current density, oxygen concentration reference, and make it contented specific relationship, polarization curve can not coincide. But when combined with certain constraints, polarization curves completely coincide.
PEMFC performance is influenced by many parameters, the research of combination parameters, not only reduced the parameter research integer, but more importantly is that one brand-new research technique is applicated in PEMFC performance optimization research, and promoted the PEMFC basic study development. Through analyzes the parameters reciprocity, it could revelation the control microscopic mechanism of battery, avoiding the sole parameter research deficiency. Through analysis the combination parameter's physics significance, it could build the foundation for deep research. Through analysis the combination parameter or the constraints and polarization curve's relations, it would give us clear direction about the battery performance optimizes.
引文
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