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The intermediate operating temperatures (~400–600 °C) of reversible protonic ceramic fuel cells (RePCFC) permit the potential use of ammonia as a carbon-neutral high energy density fuel and energy storage medium. Here we show fabrication of anode-supported RePCFC with an ultra-dense (~100%) and thin (4 μm) protonic ceramic electrolyte layer. When coupled to a novel Ru-(BaO)2(CaO)(Al2O3) (Ru-B2CA) reversible ammonia catalyst, maximum fuel-cell power generation reaches 877 mW cm−2 at 650 °C under ammonia fuel. We report relatively stable operation at 600 °C for up to 1250 h under ammonia fuel. In fuel production mode, ammonia rates exceed 1.2 × 10−8 NH3 mol cm−2 s−1at ambient pressure with H2 from electrolysis only, and 2.1 × 10−6 mol NH3 cm−2 s−1 at 12.5 bar with H2 from both electrolysis and simulated recycling gas.

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We present our efforts to scale-up proton-conducting ceramic fuel cells (PCFC) for integration into small multi-cell stacks. Proton-conducting ceramics are an exciting new class of materials that are now emerging from research laboratories to address societal challenges in electricity generation, energy storage, and fuels synthesis. While there are many technologies under investigation, intermediate temperature proton-conducting fuel cells (PCFC) have been drawing attention due to their high performance at low temperatures in fuel cell mode (up to ~2 Wcm2 at 600 ºC) and their high efficiency (90 – 98 % Faradic efficiency) when operated in electrolysis mode. However despite the impressive achievements at lab-scale PCFC technology limited investments have been made on the scaling up process due to the challenges that the PCFC fabrication procedure represents. In fact, there are no stack demonstrations reported to date in the archival literature. In this presentation we will review our efforts at Colorado School of Mines to increase the size of PCFCs beyond the button-cell level, and to integrate these cells into multi-cell stack assemblies. The stability of our PCFC stack reached the degradation rates of 3.5% and 2.1% per 1000 hours, respectively, under fuel cell and electrolysis modes. An illustration of our stack design is shown in Figure 1, and includes a photograph of a fully assembled three-cell stack after performance testing. The design is centered on three repeating components: the protonic-ceramic electrolysis cells, the composite-ceramic frames in which the cells are bonded, and the thin metallic interconnect / bipolar plates that conduct electricity between adjacent cells. The cells feature a dense, 20 μm-thick BaCe0.4Zr0.4Y0.1Yb0.1O3- d (BCZYYb4411) electrolyte on a porous Ni-BCZYYb4411 anode fabricated through reactive-sintering methods. The cathode is a novel BaCo0.4Fe0.4Zr0.1Y0.1O3-δ (BCFZY) atop of the BCZYYb4411 electrolyte with the maximum active area of ~ 7cm2 per single unit cell. Reactive gases are fed through fuel and oxidizer ports machined into the frame. The metallic interconnect is a ferritic steel developed for intermediate-temperature solid-oxide fuel cells and electrolyzers, and is compression sealed to the frame. Metallic meshes (not shown) electrically connect the electrodes to the interconnects. High protonic-ceramic cell performance operating at 550 0C has been previously demonstrated at Colorado School of Mines. While the lower operating temperature should present benefits for the long-term stability of the stack it also brings questions regarding the behavior of stack materials such as the interconnects which represent a source of degradation in performance depending on the composition of the scale that is grown on them. In an effort to better understand the root causes behind performance degradation processes in our protonic-ceramic stacks, we have integrated numerous voltage-taps throughout the stack shown in Figure 1. In this presentation, we will review our results for long-term protonic-ceramic stack operation under both fuel cell and electrolysis mode, discuss after-test interconnects analysis showing high-iron-content scale and present strategies for reducing degradation rates and extending stack life. Figure 1

Proton-conducting ceramics are emerging as an enabling material for efficient electricity generation, energy storage, and fuels synthesis. While recent advancements at the lab-scale are highly encouraging, there are few reports of scaling cell size beyond the button cell, and no demonstrations of multi-cell stacks. Through support from the U.S. Department of Energy, researchers at the Colorado School of Mines are scaling up protonic-ceramic devices from the button-cell level into small, multi-cell stacks as illustrated in the figure. Both fuel-cell and electrolyzer stacks are in development. The order-of-magnitude increases in the physical size of the delicate membrane-electrode assembly (MEA) bring concerns regarding mechanical strength and robustness. The compatibility of protonic-ceramic materials with stack-packaging materials – metallic interconnects, current collectors, glass-ceramic sealants, and gaskets – has witnessed limited study. In this presentation, we describe selection and tuning of materials, fabrication procedures, and operating conditions to achieve reasonable performance and low degradation in protonic-ceramic fuel cells (PCFCs) stacks. We find highest stack electrochemical performance and durability when utilizing electrolytes based on BaCe0.4Zr0.4Y0.1Yb0.1O3-d (BCZYYb). The anode support is a nickel-electrolyte composite, while the cathode is BaCe0.4Fe0.4Zr0.1Y0.1O3-d (BCFZY). The planar MEAs reach 5 cm2 in active area. The circular stack design enables a measure of flexibility in MEA physical size and shape, and provides balance in stress distribution from thermal- and chemical-expansion. The MEAs are packaged within ferritic-steel interconnects and macor frames to form multi-cell stacks. Our three-cell stack demonstrates encouraging performance, reaching 0.69 and 0.47 W cm-2 under H2 and CH4 fuels, respectively, at 600 ºC. A cathode-electrolyte interlayer of 10%-gadolinium-doped ceria proves critical in achieving stack degradation as low as 1.5% kh-1. Figure 1