High-Pressure Operation of Proton-Conducting Electrolyzers for High-Temperature Water Splitting

Abstract

In this work, we present our progress on high-temperature water splitting (HTWS) and hydrogen production at elevated pressure using proton-conducting ceramics. The electrochemical performance of the proton-conducting electrolyzer unit-cell stack is analyzed at 550 °C and pressures up to 12 bar.Proton-conducting ceramics are a promising new class of electrochemical cells due to their high proton conductivity at intermediate temperatures in comparison to more-conventional solid-oxide or molten-carbonate counterparts. Materials exploration continues for fabricating proton conducting cells to achieve better electrochemical performance during operation. Recently, lower ohmic resistance and degradation rates have been observed using the highly proton-conductive and chemically stable perovskite BaCe0.4 Zr0.4 Y0.1 Yb0.1 O3−δ (BCZYYb4411). In this study we work with a composite of Ni–BZCYYb4411 as the fuel electrode (cathode), BCZYYb4411 as the electrolyte and BCFZY as the steam electrode (anode). The cathode and electrolyte layers of the membrane-electrode assemblies used in this study are synthetized using the solid-state reactive sintering (SSRS) method. SSRS is an attractive MEA-fabrication method, as it greatly reduces the number of costly and time-consuming high-temperature sintering processes. During SSRS, single-phase protonic-ceramic perovskite is formed from parent oxides during high-temperature co-sintering of the anode-electrolyte layers. This is in contrast to more-traditional processing, in which the desired phase is first formed in powder form through calcination of parent oxides, while MEA formation is executed in follow-on high-temperature sintering steps.The cathode support is formed by dry-pressing to produce a 57-mm-dia x 1.5-mm-thick disc. The electrolyte (~ 10 mm) layer is deposited using an ultrasonic spray atomizer. The process control and narrow particle size distribution delivered by the ultrasonic atomizer consistently produces a high-density electrolyte, while minimizing thickness. We are now extending the use of ultrasonic spray deposition to other critical components such as the air-steam electrode and interfacial layers.As shown in Figure 1a, the protonic-ceramic membrane-electrode assembly (MEA) is bonded to a composite ceramic frame and assembled into a sealed cell stack with metallic interconnects, current collectors, sealing gaskets and end plates. The stack is placed in a preloaded spring-based mechanical compression system that axially compresses the electrolyzer stack while avoiding any direct compression of the MEA. The assembly is placed in a sealed vessel (Figure 1b); anode and cathode gas pressures are balanced across the MEA, and with the surrounding inert vessel gas (N2). Downstream back-pressure regulators maintain electrolyzer and vessel pressures to minimize the risk of cell fracture.Despite the challenges associated with high pressure operation, this technology is key to address some of the main issues associated with proton conducting ceramics. Higher pressure operation should lead to higher efficiencies by decreasing the electron hole concentration in the electrolyte usually associated with the electron leakage problem. Also, electrode activity can be enhanced at higher pressures, enabling higher currents at lower driving voltages. Figure 1c shows an increased electrolyzer performance of almost 50% when the operating pressure is raised to 12.5 bar. This is evidence of the better kinetics and lower power required to electrolyze at higher pressures.In parallel, the high-pressure protonic-ceramic electrolyzer delivers a pure, dry, pressurized hydrogen product stream that does not require downstream separation processes. Pressurized operation reduces downstream compression needs. Elevated-pressure operation is also beneficial for the synthesis of electrofuels, where green hydrogen is transformed into higher-value chemical. These chemistries often require high temperatures and pressures to achieve meaningful production rates. Ammonia serves as an example, the second-most-produced global chemical that contributes nearly 1.5% of global annual CO2 emissions. We are currently integrating our high-pressure electrolysis operation with ruthenium-based catalysts for electrochemical ammonia synthesis. In this talk, our progress in electrochemical energy storage with proton-conducting ceramics will be reviewed. Figure 1