硼氢化物燃料电池阳极催化剂研究和结构设计
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摘要
燃料电池(FC)是一种将存在于燃料与氧化剂中的化学能直接转化为电能的发电装置。硼氢化物燃料电池(DBFC)是以硼氢化物溶液为燃料,具有比一般燃料电池更高的输出电压和功率密度、可以用普通的催化剂来替代贵金属、在常温下工作等优点。而且硼氢化物是固体,具有运输、安全性等方面的巨大优势。本文研究了稀土储氢合金材料替代贵金属作为硼氢化物燃料电池阳极催化剂的可能性,并对硼氢化物在稀土系储氢合金电极表面的电化学反应过程以及机理进行深入地研究。
储氢材料跟通常的贵金属催化剂具有明显的区别,它除了具有直接催化BH_4~。氧化的能力,还能够将释放出来的氢气吸附、储存,然后再以电能的形式释放出来,因此可以提高燃料的利用率。本文以LaNi_(4.5)Al_(0.5)稀土储氢合金为对象,对该合金在硼氢化物溶液中的电化学行为和性能进行了全面的调查。确认了电解液组成、反应温度和放电电流等参数对电极性能的影响。在LaNi_(4.5)Al_(0.5)合金基础上,通过自还原反应、机械球磨和热处理相结合的方法,用Au、Ag、Si等元素对合金表面结构和元素分布进行了修饰和调整,抑制了硼氢化物水解副反应,大大提高了燃料的利用率,燃料的利用率可以达到65%,最大功率密度可达到200 mW cm~(-2)。
本文采用SEM-EDS、XRD等材料分析手段和循环伏安(CV)、交流阻抗(EIS)、极化曲线等电化学分析相结合,揭示合金材料结构、组成、形貌、颗粒尺寸大小等本征结构与电化学性能之间的关系,并对电极表面反应机理和影响因素进行深入的研究。通过对储氢合金电极表面硼氢化物反应机理的研究,发现直接8电子转化非常困难,但是可以通过4电子一次转化,然后将析出的氢再转化成质子的方法,有效的提高燃料的利用率。采用原位红外技术(in-situ IR),对放电过程中的反应进行了观察,但由于没有任何可以参考的文献资料,对其中一些红外反应峰还不能明确归属,需进一步的研究。采用量化计算的方法,研究了硼氢化物负离子脱氢反应的能量变化。结果表明,脱氢反应可以是氢氧根离子(OH~-)逐步取代氢负离子,同时析出氢气或氢正离子和电子的过程。
在直接硼氢化物燃料电池中,由于反应物的氧化分解,会在流道中产生气液两相流,增加流动阻力,减小电极的有效利用面积,给电池的稳定操作带来不利影响。为了减少硼氢化物水解产生的氢气对电池性能的影响,仿生树叶叶脉结构设计了新型的燃料电池流场板。将本设计的流场板与常见的蛇形和平行式的流场板相比较,该新型流场板不但减小了流体流动阻力,使得流体的分布更为均匀,并且将反应过程中产生的气体以最短的路径快速的排出燃料电池,从而有效的提高燃料的利用率和燃料电池的输出功率。
Fuel cell(FC) is an electrochemical conversion device which converts chemically energy from fuel and oxidant into electricity directly.The direct borohydride fuel cell (DBFC) takes borohydride solution as fuel.It has advantages such as higher theoretical voltage and power density than fuel cells with hydrogen gas as the fuel.At the same time,borohydride could be storaged and transported in a solid state or liquid state,it is much more convienient than the hydrogen.We want to explore the possibility using rare-earth hydrogen storage alloy as anodic catalysts for DBFC,and the reaction mechanism of the interface between electrode/electrolyte is also discussed in detail.
The hydrogen storage alloy used as catalyst shows excellent catalytic activity to the oxidation and hydrolysis of BH_4~-,it also can adsorb and storage the hydrogen released from BH_4~-hydrolysis and then generates electricity further,which enhance the fuel utilization.In this work,LaNi_(4.5)Al_(0.5) alloy is used as anodic catalyst for DBFC.The effect of electrolyte,reaction,temperature and discharge current on the electrochemical behaviours and electrode performance is investigated.Self-reduction, mechanical ball milling and heat treatment methods are applied to modify LaNi_(4.5)Al_(0.5) alloy with Au,Ag,and Si elements.After modification,the side reaction,the hydrolysis of BH_4~- is suppressed and fuel utilization is enhanced to 65%,the largest power density reaches to 200 mW cm~(-2).
SEM-EDS,XRD,CV,EIS and polarization curve have been carded out to reveal the relationship between material structure,composition,particle size and the electrochemical performance of hydrogen storage alloys used as the catalysts in DBFC.It found that the direct 8e conversion was quite difficult,however,4e conversion can be realized along with generating electricity further from the hydrogen released form BH_4~- hydrolysis,thus fuel utilization was enhanced.The reaction mechanism in discharge process has been observed by in-situ IR.Quantum chemistry calculation has been used to investigate the energy change for BH_4~- dehydrogenation. It is indicated that the H~-in BH_4~- could be replaced by OH~- step by step,along with the process for hydrogen evolution,or H~+ and electron generation.
The evolution of hydrogen is unavoidable in DBFC because of the hydrolysis of borohydride,which will result in a gas-liquid biphase flow in the channel of bipolar plate and reduce the touch between the catalyst and the fuel,which reduces the discharge power density.In order to lessen the effect of hydrogen released from BH_4~-, a novel bionic leaf venation structure polar plate has been designed.It found that the novel polar plate not only exhibits the minimum flow resistance and better liquid distribution,but also eliminates the gas generated from the reaction process in the most shortest path,which enhances the fuel utilization and output power.
储氢材料跟通常的贵金属催化剂具有明显的区别,它除了具有直接催化BH_4~。氧化的能力,还能够将释放出来的氢气吸附、储存,然后再以电能的形式释放出来,因此可以提高燃料的利用率。本文以LaNi_(4.5)Al_(0.5)稀土储氢合金为对象,对该合金在硼氢化物溶液中的电化学行为和性能进行了全面的调查。确认了电解液组成、反应温度和放电电流等参数对电极性能的影响。在LaNi_(4.5)Al_(0.5)合金基础上,通过自还原反应、机械球磨和热处理相结合的方法,用Au、Ag、Si等元素对合金表面结构和元素分布进行了修饰和调整,抑制了硼氢化物水解副反应,大大提高了燃料的利用率,燃料的利用率可以达到65%,最大功率密度可达到200 mW cm~(-2)。
本文采用SEM-EDS、XRD等材料分析手段和循环伏安(CV)、交流阻抗(EIS)、极化曲线等电化学分析相结合,揭示合金材料结构、组成、形貌、颗粒尺寸大小等本征结构与电化学性能之间的关系,并对电极表面反应机理和影响因素进行深入的研究。通过对储氢合金电极表面硼氢化物反应机理的研究,发现直接8电子转化非常困难,但是可以通过4电子一次转化,然后将析出的氢再转化成质子的方法,有效的提高燃料的利用率。采用原位红外技术(in-situ IR),对放电过程中的反应进行了观察,但由于没有任何可以参考的文献资料,对其中一些红外反应峰还不能明确归属,需进一步的研究。采用量化计算的方法,研究了硼氢化物负离子脱氢反应的能量变化。结果表明,脱氢反应可以是氢氧根离子(OH~-)逐步取代氢负离子,同时析出氢气或氢正离子和电子的过程。
在直接硼氢化物燃料电池中,由于反应物的氧化分解,会在流道中产生气液两相流,增加流动阻力,减小电极的有效利用面积,给电池的稳定操作带来不利影响。为了减少硼氢化物水解产生的氢气对电池性能的影响,仿生树叶叶脉结构设计了新型的燃料电池流场板。将本设计的流场板与常见的蛇形和平行式的流场板相比较,该新型流场板不但减小了流体流动阻力,使得流体的分布更为均匀,并且将反应过程中产生的气体以最短的路径快速的排出燃料电池,从而有效的提高燃料的利用率和燃料电池的输出功率。
Fuel cell(FC) is an electrochemical conversion device which converts chemically energy from fuel and oxidant into electricity directly.The direct borohydride fuel cell (DBFC) takes borohydride solution as fuel.It has advantages such as higher theoretical voltage and power density than fuel cells with hydrogen gas as the fuel.At the same time,borohydride could be storaged and transported in a solid state or liquid state,it is much more convienient than the hydrogen.We want to explore the possibility using rare-earth hydrogen storage alloy as anodic catalysts for DBFC,and the reaction mechanism of the interface between electrode/electrolyte is also discussed in detail.
The hydrogen storage alloy used as catalyst shows excellent catalytic activity to the oxidation and hydrolysis of BH_4~-,it also can adsorb and storage the hydrogen released from BH_4~-hydrolysis and then generates electricity further,which enhance the fuel utilization.In this work,LaNi_(4.5)Al_(0.5) alloy is used as anodic catalyst for DBFC.The effect of electrolyte,reaction,temperature and discharge current on the electrochemical behaviours and electrode performance is investigated.Self-reduction, mechanical ball milling and heat treatment methods are applied to modify LaNi_(4.5)Al_(0.5) alloy with Au,Ag,and Si elements.After modification,the side reaction,the hydrolysis of BH_4~- is suppressed and fuel utilization is enhanced to 65%,the largest power density reaches to 200 mW cm~(-2).
SEM-EDS,XRD,CV,EIS and polarization curve have been carded out to reveal the relationship between material structure,composition,particle size and the electrochemical performance of hydrogen storage alloys used as the catalysts in DBFC.It found that the direct 8e conversion was quite difficult,however,4e conversion can be realized along with generating electricity further from the hydrogen released form BH_4~- hydrolysis,thus fuel utilization was enhanced.The reaction mechanism in discharge process has been observed by in-situ IR.Quantum chemistry calculation has been used to investigate the energy change for BH_4~- dehydrogenation. It is indicated that the H~-in BH_4~- could be replaced by OH~- step by step,along with the process for hydrogen evolution,or H~+ and electron generation.
The evolution of hydrogen is unavoidable in DBFC because of the hydrolysis of borohydride,which will result in a gas-liquid biphase flow in the channel of bipolar plate and reduce the touch between the catalyst and the fuel,which reduces the discharge power density.In order to lessen the effect of hydrogen released from BH_4~-, a novel bionic leaf venation structure polar plate has been designed.It found that the novel polar plate not only exhibits the minimum flow resistance and better liquid distribution,but also eliminates the gas generated from the reaction process in the most shortest path,which enhances the fuel utilization and output power.
引文
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