质子交换膜燃料电池自增湿膜电极的制备与研究
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摘要
随着化石燃料的日趋枯竭以及化石燃料燃烧所引起的环境危机日益加剧，新能源以及新的能源利用方式引起了人们越来越多的关注。质子交换膜燃料电池（PEMFC）因其比能量高、无污染、可低温快速启动等优点而受到人们的广泛关注。膜电极（MEA）是质子交换膜燃料电池的核心部件，不仅对燃料电池的性能有很大的影响，而且对降低其生产成本、加快其商业化进程具有很重要的现实意义。杜邦公司生产的商业Nafion系列质子交换膜由于其良好的机械稳定性和热稳定，以及高质子传导率，被广泛的应用于质子交换膜燃料电池的电解质膜。Nafion膜和催化层中的Nafion树脂均需要充足的水份来维持其较高的电导率，湿度的降低会导致质子交换膜的质子传导率下降以及电池内阻增大，进而使电池性能下降。在质子交换膜燃料电池的实际运行中，常需要借助于外增湿设备，使氢气和氧气在进入电池之前带入水蒸气，从而对电池系统进行增湿。然而，这会导致燃料电池系统复杂化、成本升高，以及系统的能量效率和体积比能量密度降低。因此，自增湿膜电极是质子交换膜燃料电池研究领域的最为重要的追求目标之一。实现膜电极的免增湿，不仅可以解决目前质子交换膜燃料电池的水热管理困难的难题，还能通过抛除外增湿设备以达到大幅度降低燃料电池系统成本、减少燃料电池系统自身能量消耗的目的，对于质子交换膜燃料电池商业化具有极其重要的意义。
本文从提高质子交换膜燃料电池膜电极在低湿度下的性能以及稳定性出发，采用亲水性的有机高分子聚合物为保水剂，将其添加到阴/阳极催化层，制备自增湿膜电极；采用层层自组装技术将亲水性的聚电解质（PANI）和二氧化硅组装到Nafion膜上，形成自增湿复合膜，并制备成自增湿膜电极。
首先，采用亲水性的有机高分子聚合物添加到阳极催化层中，制备自增湿膜电极。考察了亲水性有机高分子聚合物的种类，添加量以及阴阳极相对湿度对自增湿膜电极性能的影响。结果表明：采用PVA为保水剂的自增湿膜电极的电池性能较使用其他类型的高分子聚合物为保水剂的好；PVA的添加会提高阳极催化层的润湿程度和含水率，而5wt.%的添加量是阳极催化层中PVA的最佳含量；改变阴阳极的相对湿度对自增湿膜电极的性能影响不大；在电池温度为50oC，阴阳极相对湿度为34%，气体背压为20psi的条件下，PVA添加量为5wt.%的自增湿膜电极在0.7V和0.6V时的电流密度分别可以达到600mA.cm~(-2)和1000mA.cm~(-2)，经过长达60小时的长时间恒电压放电测试，在0.6V下的电流密度仍可维持在750-780mA.cm~(-2)左右。
其次，提高电池温度有利于提高催化剂的活性以及简化水热管理，但这同时对燃料电池在低湿度下的稳定运行提出了挑战。为了解决在高温、低湿度下保持Nafion膜较高的质子传导率与提高催化剂活性之间的内在矛盾。我们采用亲水性的有机高分子聚合物（PVA）和无机氧化物（SiO_2）同时添加到阳极催化层中，制备在较高电池温度下仍具有良好低湿度性能的自增湿膜电极。结果表明：采用PVA和SiO_2同时添加到阳极催化层所制备的自增湿膜电极性能优于单独采用PVA或SiO_2为保水剂的自增湿膜电极。当电池处于60oC和15%的湿度下运行时，PVA和SiO_2的添加量为3wt.%的膜电极MPS3，在0.6V下的电流密度可以达到1100mA.cm~(-2)，且最大的功率密度为780mW.cm~(-2)。适当的提高电池温度有利于电池性能的提升。当阴阳极相对湿度从100%下降至15%，膜电极的性能几乎没有发生太大的变化。在电池温度为60oC下，自增湿膜电极MPS3表现出良好的低湿度运行稳定性，在15%的相对湿度下，经过30小时的长时间恒电压放电之后，其在0.6V下的电流密度下降幅度很小，仅由1100mA.cm~(-2)降低至900mA.cm~(-2)左右，而阳极仅添加PVA和SiO_2的样品，其电流密度仅为700mA.cm~(-2)和800mA.cm~(-2)。
再者，我们采用特殊的双层阴极结构，将亲水性的有机高分子聚合物（PVA）添加到阴极内层催化层中制备自增湿膜电极。在氢-空燃料电池中，我们对PVA在阴极催化层中的添加方式，PVA的添加量、电池温度以及阴阳极相对湿度对该特殊结构的自增湿膜电极在低湿度下的性能进行了评价。结果表明：与将PVA添加到单层阴极催化层和双层阴极结构的外层催化层中相比，将PVA添加到双层阴极结构的内层催化层的自增湿膜电极，尽管在完全增湿情况下会增大电池的浓差极化，但是在低湿度下易于增强水的反扩散，有利于保持质子交换膜在低湿度下处于良好的润湿状态。在电池温度为60oC，气体背压为30psi，阴阳极相对湿度为20%时，将PVA添加到双层阴极结构的内层催化层中的自增湿膜电极在0.6V下的电流密度可以达到900mA.cm~(-2)，是将PVA添加到双层阴极结构的外层催化层的自增湿膜电极的2.25倍，而将比单层阴极结构的自增湿膜电极高出3.5倍。
最后，我们将层层自组装技术应用于制备自增湿复合膜，采用掺杂聚苯胺和SiO_2以静电结合的方式层层组装到Nafion膜上，制备成Nafion/(PANI/SiO_2)n型复合膜。采用数码照片、热重分析、傅里叶红外变换光谱、紫外-可见光吸收光谱、X-射线衍射等手段对自增湿复合膜进行表征。结果发现：PANI和SiO_2可以成功的被吸附到Nafion膜上，且PANI的含量与自组装层数成正比关系。电导率测试发现随着自组装层数的增加，复合膜的质子传导率逐渐降低。电池性能测试表明：当（PANI/SiO_2）的复合层数为7层时，膜电极在低湿度下的电池性能最好。
With the drying up of fossil fuels and the serious problem of environmental pollutioncaused by the combustion of fossil fuels，more and more attention has been paid to thedevelopment of new energy and new energy utilization technology. Proton exchangemembrane fuel cells (PEMFCs) have becoming attractive due to their advantages, such ashigh power density, zero or low exhaust, and quick startup at low temperature, etc. Membraneelectrode assembly (MEA) is the key component of PEMFC, it not only plays a key role forthe performance of the PEMFCs, but also for the reducing the cost of the fuel cells, as well asaccelerating the commercial applications. The commercial Nafion series membranes producedby Dupont company (USA) are commonly applied to the electrolyte because of its goodmechanical and thermal stability, as well as its high proton conductivity at100%relativehumidity (RH). Actually, Nafion ionomer is also used in the catalyst layer as a binder andproton conductor. However, the proton conductivity of Nafion depends strongly on the watercontent; dehydration of the Nafion membrane will lead to a series of detrimental effects on thePEMFC’s performance. The proton conductivity of Nafion membrane will decrease and theohmic resistance of the cell will increase under low-humidity conditions, causing rapid decayin cell performance. Thus, in terms of the actual operating conditions of a PEMFC, anexternal humidifier has to be used to maintain the water content of the cell system. In otherwords, the reactant gas must pass through the external humidifier and absorb water vaporbefore entering the cell. Therefore, this approach makes the cell system complicated, makesits energy efficiency and volume efficiency reduced, and makes the cost of fuel cell increased,thereby hinders the commercialization of the fuel cells. Indeed, the development of aself-humidifying membrane electrode assembly (MEA) has become one of the most importantsubjects in the PEMFC field. It is a most important aim for PEMFC to realizeself-humidification or no humidification, which not only solves the problem of watermanagement in PEMFC, but also decreases the cost and self energy consumption of PEMFCsystem by reducing the external humidifier. Summarily, the development of self-humidifyingMEA is extremely significant for the development and commercialization of proton exchangemembrane fuel cell.
In this thesis, the self-humidifying MEAs were prepared by several new methods, includingadding hydrophilic organic polymer in catalyst layer, adding hydrophilic organic polymer andinorganic oxide in the catalyst layer, adding hydrophilic organic polymer in double cathodecatalyst layer, as well as preparing a self-humidification composite membrane by alayer-by-layer assembly methods.
Firstly, we prepared a novel self-humidifying membrane electrode assembly (MEA) withaddition of polyvinyl alcohol (PVA) as the hygroscopic agent into anode catalyst layer wasdeveloped for proton exchange membrane fuel cell (PEMFC). The effect of the variety ofhydrophilic organic polymer, addition amount and the relative humidity of anode and cathodewere investigated. We found that the performance of self-humidifying MEA prepared byusing PVA as hygroscopic agent is better than using other organic polymers. The waterretention ability of self-humidifying MEAs was enhanced by adding PVA in anode catalystlayer. It is interesting that the performance of MEA PVA5hardly changes even if the relativehumidity (RH) of both the anode and cathode decreased from100%to34%. The MEAsshowed good self humidification performance, for the sample with PVA addition of5wt.%(MEA PVA5), the maximum power density can reach up to623.3mW.cm~(-2), with currentdensities of1000mA.cm~(-2)at0.6V and600mA.cm~(-2)at0.7V respectively, at50oC and34%of relative humidity (RH). The MEA PVA5also showed good stability at low humidityoperating conditions: keeping the MEA discharged at constant voltage of0.6V for60hours at34%of RH, the attenuation of the current density is less than10%, whilst for the MEAwithout addition of PVA, the attenuation is high up to80%within5hours.
Secondly, the activity of catalyst increased with the increasing of cell temperature, as wellas heat and water management would be simplified at an elevated temperarue. To decrease theconflict between improving activity of catalyst and maintaining Nafion with a good protonconductivity at an elevated cell temperature under low-humidity conditions. A novelself-humidifying membrane electrode assembly (MEA) has been successfully prepared bysimultaneously adding both a hydrophilic organic polymer (polyvinyl alcohol, PVA) and aninorganic oxide (silica) to the anode catalyst layer. Compared to the self-humidifying MEA byadding only a hygroscopic substance (PVA or SiO_2) in anode catalyst layer, this MEA showedexcellent self-humidification performance under low-humidity conditions. A sample (MPS3) containing3wt.%PVA and3wt.%silica in the anode catalyst layer achieves a currentdensity as high as1100mA.cm~(-2)at0.6V, and the highest peak power density was780mW.cm~(-2), operating at60oC and15%relative humidity for both anode and cathode. Theperformance of the self-humidifying MEA was hardly changed even if the RHs of both theanode and cathode decreased from100%to15%at60oC. Appropriate to improve the celltemperature is advantageous to the promotion of cell performance. The sample also showedexcellent stability at low-humidity: after30h of continuous operation under the sameconditions, the current density decreases just slightly, from1100mA.cm~(-2)to ca.900mA.cm~(-2),whereas with MEAs to which only PVA or silica alone had been added, the current densitiesafter30h is just700mA.cm~(-2)and800mA.cm~(-2), respectively.
Furthermore, a self-humidifying MEA was prepared by adding hydrophilic organic polymer(PVA) in the inner layer of the double cathode catalyst layer. The effect of adding mode ofPVA in the cathode, the addition amount, the cell temperature and the relative humidity ofanode and cathode were investigated. Compared to the MEA by adding PVA in the singlecathode layer (SC-3PVA) and adding PVA in the outlayer of double cathode layer(DC-3PVA-outer), the concentration polarization was increaed by adding PVA in the innerlayer of double cathode layer (DC-3PVA-inner), but the back diffusion of water from cathodeto anode was enhanced. At a cell temperature of60oC and30psi, the current density ofDC-3PVA-inner at0.6V can achieved900mA.cm~(-2)at20%RH, which is2.25times higherthan that of DC-3PVA-outer and4.5times higher than that of SC-3PVA.
Finally, a novel self-humidifying composite membrane Nafion/(PANI/SiO_2)n was preparedby layer-by-layer assembly using doped PANI and SiO_2as the raw substances. We suggestedthat the doped PANI and SiO_2assemble on the Nafion membran in a form of electrostaticattraction. The composite membranes were characterized by Digital photos,Thermogravimetric analysis (TG), Fourier transform infrared spectroscopy (FTIR),Ultraviolet-visible absorption spectrum (UV-vis), X-ray diffraction (XRD). We found that thedoped PANI and SiO_2can be successful absorbed on the Nafion membrane, and theadsorption quantity of PANI is proportional to the assemble layer. The proton conductivity ofcomposite membranes gradually decreased with the increaing of (PANI/SiO_2) layers byelectrical conductivity tests. When the (PANI/SiO_2) layers is7, the cell performance of self-humidifying MEA is the best in the low humidity condition.
本文从提高质子交换膜燃料电池膜电极在低湿度下的性能以及稳定性出发，采用亲水性的有机高分子聚合物为保水剂，将其添加到阴/阳极催化层，制备自增湿膜电极；采用层层自组装技术将亲水性的聚电解质（PANI）和二氧化硅组装到Nafion膜上，形成自增湿复合膜，并制备成自增湿膜电极。
首先，采用亲水性的有机高分子聚合物添加到阳极催化层中，制备自增湿膜电极。考察了亲水性有机高分子聚合物的种类，添加量以及阴阳极相对湿度对自增湿膜电极性能的影响。结果表明：采用PVA为保水剂的自增湿膜电极的电池性能较使用其他类型的高分子聚合物为保水剂的好；PVA的添加会提高阳极催化层的润湿程度和含水率，而5wt.%的添加量是阳极催化层中PVA的最佳含量；改变阴阳极的相对湿度对自增湿膜电极的性能影响不大；在电池温度为50oC，阴阳极相对湿度为34%，气体背压为20psi的条件下，PVA添加量为5wt.%的自增湿膜电极在0.7V和0.6V时的电流密度分别可以达到600mA.cm~(-2)和1000mA.cm~(-2)，经过长达60小时的长时间恒电压放电测试，在0.6V下的电流密度仍可维持在750-780mA.cm~(-2)左右。
其次，提高电池温度有利于提高催化剂的活性以及简化水热管理，但这同时对燃料电池在低湿度下的稳定运行提出了挑战。为了解决在高温、低湿度下保持Nafion膜较高的质子传导率与提高催化剂活性之间的内在矛盾。我们采用亲水性的有机高分子聚合物（PVA）和无机氧化物（SiO_2）同时添加到阳极催化层中，制备在较高电池温度下仍具有良好低湿度性能的自增湿膜电极。结果表明：采用PVA和SiO_2同时添加到阳极催化层所制备的自增湿膜电极性能优于单独采用PVA或SiO_2为保水剂的自增湿膜电极。当电池处于60oC和15%的湿度下运行时，PVA和SiO_2的添加量为3wt.%的膜电极MPS3，在0.6V下的电流密度可以达到1100mA.cm~(-2)，且最大的功率密度为780mW.cm~(-2)。适当的提高电池温度有利于电池性能的提升。当阴阳极相对湿度从100%下降至15%，膜电极的性能几乎没有发生太大的变化。在电池温度为60oC下，自增湿膜电极MPS3表现出良好的低湿度运行稳定性，在15%的相对湿度下，经过30小时的长时间恒电压放电之后，其在0.6V下的电流密度下降幅度很小，仅由1100mA.cm~(-2)降低至900mA.cm~(-2)左右，而阳极仅添加PVA和SiO_2的样品，其电流密度仅为700mA.cm~(-2)和800mA.cm~(-2)。
再者，我们采用特殊的双层阴极结构，将亲水性的有机高分子聚合物（PVA）添加到阴极内层催化层中制备自增湿膜电极。在氢-空燃料电池中，我们对PVA在阴极催化层中的添加方式，PVA的添加量、电池温度以及阴阳极相对湿度对该特殊结构的自增湿膜电极在低湿度下的性能进行了评价。结果表明：与将PVA添加到单层阴极催化层和双层阴极结构的外层催化层中相比，将PVA添加到双层阴极结构的内层催化层的自增湿膜电极，尽管在完全增湿情况下会增大电池的浓差极化，但是在低湿度下易于增强水的反扩散，有利于保持质子交换膜在低湿度下处于良好的润湿状态。在电池温度为60oC，气体背压为30psi，阴阳极相对湿度为20%时，将PVA添加到双层阴极结构的内层催化层中的自增湿膜电极在0.6V下的电流密度可以达到900mA.cm~(-2)，是将PVA添加到双层阴极结构的外层催化层的自增湿膜电极的2.25倍，而将比单层阴极结构的自增湿膜电极高出3.5倍。
最后，我们将层层自组装技术应用于制备自增湿复合膜，采用掺杂聚苯胺和SiO_2以静电结合的方式层层组装到Nafion膜上，制备成Nafion/(PANI/SiO_2)n型复合膜。采用数码照片、热重分析、傅里叶红外变换光谱、紫外-可见光吸收光谱、X-射线衍射等手段对自增湿复合膜进行表征。结果发现：PANI和SiO_2可以成功的被吸附到Nafion膜上，且PANI的含量与自组装层数成正比关系。电导率测试发现随着自组装层数的增加，复合膜的质子传导率逐渐降低。电池性能测试表明：当（PANI/SiO_2）的复合层数为7层时，膜电极在低湿度下的电池性能最好。
With the drying up of fossil fuels and the serious problem of environmental pollutioncaused by the combustion of fossil fuels，more and more attention has been paid to thedevelopment of new energy and new energy utilization technology. Proton exchangemembrane fuel cells (PEMFCs) have becoming attractive due to their advantages, such ashigh power density, zero or low exhaust, and quick startup at low temperature, etc. Membraneelectrode assembly (MEA) is the key component of PEMFC, it not only plays a key role forthe performance of the PEMFCs, but also for the reducing the cost of the fuel cells, as well asaccelerating the commercial applications. The commercial Nafion series membranes producedby Dupont company (USA) are commonly applied to the electrolyte because of its goodmechanical and thermal stability, as well as its high proton conductivity at100%relativehumidity (RH). Actually, Nafion ionomer is also used in the catalyst layer as a binder andproton conductor. However, the proton conductivity of Nafion depends strongly on the watercontent; dehydration of the Nafion membrane will lead to a series of detrimental effects on thePEMFC’s performance. The proton conductivity of Nafion membrane will decrease and theohmic resistance of the cell will increase under low-humidity conditions, causing rapid decayin cell performance. Thus, in terms of the actual operating conditions of a PEMFC, anexternal humidifier has to be used to maintain the water content of the cell system. In otherwords, the reactant gas must pass through the external humidifier and absorb water vaporbefore entering the cell. Therefore, this approach makes the cell system complicated, makesits energy efficiency and volume efficiency reduced, and makes the cost of fuel cell increased,thereby hinders the commercialization of the fuel cells. Indeed, the development of aself-humidifying membrane electrode assembly (MEA) has become one of the most importantsubjects in the PEMFC field. It is a most important aim for PEMFC to realizeself-humidification or no humidification, which not only solves the problem of watermanagement in PEMFC, but also decreases the cost and self energy consumption of PEMFCsystem by reducing the external humidifier. Summarily, the development of self-humidifyingMEA is extremely significant for the development and commercialization of proton exchangemembrane fuel cell.
In this thesis, the self-humidifying MEAs were prepared by several new methods, includingadding hydrophilic organic polymer in catalyst layer, adding hydrophilic organic polymer andinorganic oxide in the catalyst layer, adding hydrophilic organic polymer in double cathodecatalyst layer, as well as preparing a self-humidification composite membrane by alayer-by-layer assembly methods.
Firstly, we prepared a novel self-humidifying membrane electrode assembly (MEA) withaddition of polyvinyl alcohol (PVA) as the hygroscopic agent into anode catalyst layer wasdeveloped for proton exchange membrane fuel cell (PEMFC). The effect of the variety ofhydrophilic organic polymer, addition amount and the relative humidity of anode and cathodewere investigated. We found that the performance of self-humidifying MEA prepared byusing PVA as hygroscopic agent is better than using other organic polymers. The waterretention ability of self-humidifying MEAs was enhanced by adding PVA in anode catalystlayer. It is interesting that the performance of MEA PVA5hardly changes even if the relativehumidity (RH) of both the anode and cathode decreased from100%to34%. The MEAsshowed good self humidification performance, for the sample with PVA addition of5wt.%(MEA PVA5), the maximum power density can reach up to623.3mW.cm~(-2), with currentdensities of1000mA.cm~(-2)at0.6V and600mA.cm~(-2)at0.7V respectively, at50oC and34%of relative humidity (RH). The MEA PVA5also showed good stability at low humidityoperating conditions: keeping the MEA discharged at constant voltage of0.6V for60hours at34%of RH, the attenuation of the current density is less than10%, whilst for the MEAwithout addition of PVA, the attenuation is high up to80%within5hours.
Secondly, the activity of catalyst increased with the increasing of cell temperature, as wellas heat and water management would be simplified at an elevated temperarue. To decrease theconflict between improving activity of catalyst and maintaining Nafion with a good protonconductivity at an elevated cell temperature under low-humidity conditions. A novelself-humidifying membrane electrode assembly (MEA) has been successfully prepared bysimultaneously adding both a hydrophilic organic polymer (polyvinyl alcohol, PVA) and aninorganic oxide (silica) to the anode catalyst layer. Compared to the self-humidifying MEA byadding only a hygroscopic substance (PVA or SiO_2) in anode catalyst layer, this MEA showedexcellent self-humidification performance under low-humidity conditions. A sample (MPS3) containing3wt.%PVA and3wt.%silica in the anode catalyst layer achieves a currentdensity as high as1100mA.cm~(-2)at0.6V, and the highest peak power density was780mW.cm~(-2), operating at60oC and15%relative humidity for both anode and cathode. Theperformance of the self-humidifying MEA was hardly changed even if the RHs of both theanode and cathode decreased from100%to15%at60oC. Appropriate to improve the celltemperature is advantageous to the promotion of cell performance. The sample also showedexcellent stability at low-humidity: after30h of continuous operation under the sameconditions, the current density decreases just slightly, from1100mA.cm~(-2)to ca.900mA.cm~(-2),whereas with MEAs to which only PVA or silica alone had been added, the current densitiesafter30h is just700mA.cm~(-2)and800mA.cm~(-2), respectively.
Furthermore, a self-humidifying MEA was prepared by adding hydrophilic organic polymer(PVA) in the inner layer of the double cathode catalyst layer. The effect of adding mode ofPVA in the cathode, the addition amount, the cell temperature and the relative humidity ofanode and cathode were investigated. Compared to the MEA by adding PVA in the singlecathode layer (SC-3PVA) and adding PVA in the outlayer of double cathode layer(DC-3PVA-outer), the concentration polarization was increaed by adding PVA in the innerlayer of double cathode layer (DC-3PVA-inner), but the back diffusion of water from cathodeto anode was enhanced. At a cell temperature of60oC and30psi, the current density ofDC-3PVA-inner at0.6V can achieved900mA.cm~(-2)at20%RH, which is2.25times higherthan that of DC-3PVA-outer and4.5times higher than that of SC-3PVA.
Finally, a novel self-humidifying composite membrane Nafion/(PANI/SiO_2)n was preparedby layer-by-layer assembly using doped PANI and SiO_2as the raw substances. We suggestedthat the doped PANI and SiO_2assemble on the Nafion membran in a form of electrostaticattraction. The composite membranes were characterized by Digital photos,Thermogravimetric analysis (TG), Fourier transform infrared spectroscopy (FTIR),Ultraviolet-visible absorption spectrum (UV-vis), X-ray diffraction (XRD). We found that thedoped PANI and SiO_2can be successful absorbed on the Nafion membrane, and theadsorption quantity of PANI is proportional to the assemble layer. The proton conductivity ofcomposite membranes gradually decreased with the increaing of (PANI/SiO_2) layers byelectrical conductivity tests. When the (PANI/SiO_2) layers is7, the cell performance of self-humidifying MEA is the best in the low humidity condition.
引文
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