Renewable Hydrogen Production via Thermochemical/Electrochemical Coupling

S. Babiniec, A. Ambrosini, James E Miller
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Abstract

A coupled thermochemical/electrochemical cycle was investigated to produce hydrogen from renewable resources. Like a conventional thermochemical cycle, this approach leverages chemical energy stored in a thermochemical working material that is reduced thermally by solar energy. However, in this concept, the stored chemical energy provides only a fraction of the energy required for effectively splitting steam to produce hydrogen. To push the reaction towards completion, an electrically-assisted proton-conducting membrane is employed to separate and recover hydrogen as it is produced. This novel coupled-cycle concept provides several benefits. First, the required oxidation enthalpy of the reversible thermochemical material is decreased, enabling the process to occur at lower temperatures. Second, removing the requirement for spontaneous steam splitting widens the scope of materials compositions, allowing for less expensive/more abundant elements to be used. Lastly, thermodynamics calculations suggest that this concept can potentially reach higher efficiencies than photovoltaic-to-electrolysis hydrogen production. A novel thermochemical/electrochemical test stand was conceptualized and constructed to prove the concept, and the practical feasibility of the proposed coupled cycle was assessed by validating the individual components of the system: proton conduction across a BaCe0.1Zr0.8Y0.1O3-δ (BCZY18) membrane, thermochemical activity of the CaAl0.2Mn0.8O3−δ (CAM28) working material reduced at 650 °C, and indirect observation of hydrogen production.
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通过热化学/电化学耦合可再生制氢
研究了利用可再生资源制备氢气的热化学/电化学耦合循环。像传统的热化学循环一样,这种方法利用了储存在热化学工作材料中的化学能,这种材料被太阳能热还原。然而,在这个概念中,储存的化学能只提供有效分解蒸汽产生氢所需能量的一小部分。为了推动反应的完成,一种电辅助质子传导膜被用来分离和回收产生的氢。这种新颖的耦合循环概念提供了几个好处。首先,可逆热化学材料所需的氧化焓降低,使该过程能够在较低的温度下进行。其次,消除自发蒸汽分裂的要求扩大了材料成分的范围,允许使用更便宜/更丰富的元素。最后,热力学计算表明,这一概念可能达到比光伏电解制氢更高的效率。为了验证这一概念,我们构想并构建了一个新的热化学/电化学试验台,并通过验证系统的各个组成部分来评估所提出的耦合循环的实际可行性:质子在BaCe0.1Zr0.8Y0.1O3-δ (BCZY18)膜上的传导,在650°C下降低CaAl0.2Mn0.8O3 -δ (CAM28)工作材料的热化学活性,以及间接观察氢气的产生。
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