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At least 19 records

Proton-conducting ceramic fuel cell architecture

A method of manufacturing a proton-conducting fuel cell includes assembling a green anode-electrolyte half-cell by forming an anode substrate layer having an upper surface and a lower surface, forming an anode functional layer on the upper surface of the anode substrate layer, forming an electrolyte layer on an upper surface of the anode functional layer, and forming a stress balancing layer on the lower surface of the anode substrate layer. The method further includes positioning the green anode-electrolyte half-cell on kiln furniture inside a sintering kiln and sintering the green anode-electrolyte half-cell using SSRS to an anode-electrolyte half-cell.

Wood, Anthony↗

Performance degradation in proton-conducting ceramic fuel cell and electrolyzer stacks

Proton-conducting ceramics are emerging as enabling materials for efficient electrochemical electricity generation, energy storage, and fuels synthesis. In this work, we present longer-term degradation results for protonic-ceramic fuel cells and electrolyzers based on a BaCe 0.4 Zr 0.4 Y 0.1 Yb 0.1 O 3-δ (BCZYYb) electrolyte. The cells are packaged within unit-cell stacks, including metallic interconnects, current collectors, sealing glasses and gaskets. Durability is found to be superior in protonic-ceramic electrolyzers in comparison to fuel cells. Operating conditions have a large impact on degradation rates; better stability is found at fuel-cell operating temperatures above 600 °C, and electrolyzer steam feeds below 20%. Here, we find that both fuel-cell and electrolyzer degradation is greatly reduced via the introduction of a gadolinium-doped ceria interlayer between the electrolyte and the air–steam electrode. Fuel-cell degradation falls to 1.2% khr –1 under methane fuel at 600 °C; electrolyzer degradation is reduced to 1% khr –1 at 550 °C and 50% steam. Further analyses of electrochemical impedance spectroscopy and distribution of relaxation times provide insight to root processes and degradation phenomena in protonic electroceramics.

25 ENERGY STORAGE↗

Revealing Phase Heterogeneity in Vertically Aligned Nanocomposites via Plan-View Electron Energy Loss Spectroscopy

Hydrogen utilization in clean energy technologies is challenged by limited storage and transport within materials, owing to the complex hydrogen kinetics at interfaces [1]. Understanding these interfacial mechanisms at the nanoscale is crucial for developing improved materials for hydrogen applications, particularly proton-conducting fuel cells (PCFCs). Vertically aligned nanocomposites (VANs) grown by pulsed laser deposition (PLD) offer a unique platform for investigating the interfacial effects on hydrogen transport due to their well-defined interfaces parallel to the direction of charge transport [2-4]. To investigate hydrogen transport, the two phases within the VANs were chosen as BaZr 0.9 Y 0.1 O 3-x (BZY), a known proton conductor, and Pr 0.1 Ce 0.9 O 2-x (PCO), a mixed ionic-electronic conductor [5]. This PCO-BZY VANs architecture allows the investigation of how the interface between a proton conductor and a mixed conductor influences hydrogen transport. However, because of the small size of hydrogen, it is difficult to discern the nature of its interactions with interfaces from bulk measurements at the macroscale, thus necessitating nanoscale measurements [6]. Electron energy loss spectroscopy (EELS) allows for nanometer-resolution probing of the local atomic structure and chemistry at the BZY/PCO interface. In this study, plan-view analysis of PCO-BZY VANs films was employed to characterize the structure and phase distribution of the VANs and investigate the interface between the nanostructures. The films were imaged using scanning electron microscopy (SEM) in the Hitachi S-4800 SEM, collecting secondary electron images using mixed upper and lower detectors. Then, plan-view transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM) EELS were employed using a JEOL ARM300 microscope operated at 300kV with a Gatan K3 GIF Continuum detector to study the distribution of the BZY and PCO phases through the film. As a result, spectrum images were acquired at a dispersion of 0.18eV per channel and denoised afterward by principal component analysis (PCA) method.

Griffin, Elizabeth [Northwestern University, Evans↗

Synthesis and Photonic Sintering of Proton Conducting Lanthanide Nickelates

Lanthanide nickelate perovskites are known proton conductors at intermediate temperatures (350-600°C). They are attractive targets for proton conducting fuel cells and electrolyzers due to their operational temperature range and their stability in the presence of CO 2 . These materials have the formula LNiO 3 , with the lanthanide L = La, Ce, Pr, Nd, or Sm. Sintering is challenging due to phase transformations that occur at lower temperatures than those required for sintering. In this project, a series of lanthanide nickelate perovskites was synthesized via both a precursor solid solution method and the glycine nitrate process. Powders derived from the precursor solid solution method for LaNiO 3 and NdNiO 3 were sintered at Utility Global Inc. at various temperatures utilizing fast photonic sintering. LaNiO 3 was successfully sintered while maintaining the perovskite phase. NdNiO 3 underwent a phase transformation at all the conditions tested. The stability of the perovskite phase decreases moving right across the lanthanides in the periodic table, while the expected proton conductivity increases. These results will inform further investigations into lanthanide nickelate perovskites toward the goal of producing a free-standing, sintered, proton-conducting membrane.

36 MATERIALS SCIENCE↗

Role of phosphate source in improving the proton conductivity of tin pyrophosphate and its composite electrolytes

Metal pyrophosphates (MPPs) in general, and tin pyrophosphate (TPP) in particular, have received significant interest in the last decade due to their potential as proton conductors for electrolyte application in intermediate temperature (IT)-fuel cells. However, for MPP based electrolytes, despite high reported proton conductivities, achieving good fuel cell performance and high open circuit voltage (OCV) remains a challenge with synthesis methods playing a crucial role in determining the final proton conductivity. Here we report the role of phosphate precursor in determining the TPP proton conductivity by examining five different precursors: (1) phosphoric acid (TPP-PA), (2) ammonium hydroxide + phosphoric acid (TPP-NH 4 OH), (3) diammonium phosphate (TPP-DAP), (4) tetramethylammonium sulphate + phosphoric acid (TPP-TMAP), and (5) tetrabutylammonium phosphate (TPP-TBAP), where a maximum conductivity of 88 mS cm -1 at 200 °C was obtained for TPP prepared from the TBAP precursor. TPP prepared from all of the different precursors formed the crystalline cubic Pa-3 with combining macron] phase after sintering at 650 °C for 2.5 hours. Furthermore, TPP-TBAP/Nafion® composite membranes prepared with a 90 : 10 ratio exhibited an OCV of 0.98 V and produced a maximum peak power density (PPD) of 630 mW cm -2 at an operating temperature of 220 °C. Our results demonstrate the significant impact of the TPP precursor on proton conductivity and fuel cell performance.

36 MATERIALS SCIENCE↗

Identifying Spectral Descriptors for Protonation in BaZr 0.8 Y 0.2 O 3-x with Electron Energy Loss Spectroscopy

Hydrogen economy is of paramount importance in the global transition to a sustainable, clean energy source that contributes to decarbonization efforts. In particular, the proton conducting proton ceramic fuel cells (PCFCs) play a crucial role in promoting hydrogen energy technology [1-5]. In a PCFC, the electrolyte is typically a solid oxide material that enables proton transport and can operate at temperatures lower than those of traditional oxygen ion conducting fuel cells [6]. The reduced operating temperature of PCFCs contributes to their durability, scalability, and efficiency [7,8]. BaZr 0.8 Y 0.2 O 3-x (BZY) is a promising proton conducting solid oxide electrolyte [9,10]. The emphasis on proton conductivity entails the importance of understanding proton content in the system. However, previous studies have largely relied on bulk techniques such as electrochemical impedance spectroscopy [7,11], Karl-Fischer titration [12,13], and thermogravimetric analysis [14] to obtain proton concentration. This is due to the small atomic size and light mass of hydrogen species making direct detection challenging. Bulk methods may be useful in estimating the proton content; however, it overlooks possible proton concentration gradient or segregation that may occur across or within a nanoparticle, especially when proton incorporation occurs nonuniformly through steam exposure on powder samples. In this paper, BZY is protonated at an estimated 0.15 mol of protons via steam exposure. Electron energy loss spectroscopy (EELS) with nanoscale spatial resolution is explored to identify proxy signals for proton detection using a JEOL ARM300 microscope operated at 300 kV with a Gatan GIF Continuum detector.

08 HYDROGEN↗

The Effect of Proton Conductivity of Fe–N–C–Based Cathode on PEM Fuel cell Performance

A model–based impedance spectroscopy is used to determine proton conductivity, oxygen transport parameter, double layer capacitance and oxygen reduction reaction (ORR) Tafel slope in the Fe–N–C cathode catalyst layer (CCL) of a PEM fuel cell. Experimental spectra of two cells differing by the membrane thickness only are processed using a physics–based model for PEMFC impedance. The spectra have been measured in the range of current densities from 25 to 800 mA cm -2 . The ORR Tafel slope of both the cells shows almost linear growth with the current density. In one of the cells, the CCL proton conductivity σp strongly decays at the current density of 100 mA cm -2 ; this decay is accompanied by the step growth of the double layer capacitance. Other minor variations of proton conductivity and double layer capacitance with the cell current occur also in a counterphase; presumed origin of this effect is discussed. The oxygen diffusion coefficient in the cathode exhibits explosive growth with the cell current. We attribute this effect to formation of temperature and pressure gradients in the CCL due to strongly non–uniform distribution of ORR rate in the electrode.

25 ENERGY STORAGE↗

Protonated phosphonic acid electrodes for high power heavy-duty vehicle fuel cells

We report that state-of-the-art automotive fuel cells that operate at about 80 °C require large radiators and air intakes to avoid overheating. High-temperature fuel cells that operate above 100 °C under anhydrous conditions provide an ideal solution for heat rejection in heavy-duty vehicle applications. Here we report protonated phosphonic acid electrodes that remarkably improve the performance of high-temperature polymer electrolyte membrane fuel cells. The protonated phosphonic acids comprise tetrafluorostyrene-phosphonic acid and perfluorosulfonic acid polymers, where a perfluorosulfonic acid proton is transferred to the phosphonic acid to enhance the anhydrous proton conduction of fuel cell electrodes. By using this material in fuel cell electrodes, we obtained a fuel cell exhibiting a rated power density of 780 mW cm -2 at 160 °C, with minimal degradation during 2,500 h of operation and 700 thermal cycles from 40 to 160 °C under load.

25 ENERGY STORAGE↗

Improving tubular protonic ceramic fuel cell performance by compensating Ba evaporation via a Ba-excess optimized proton conducting electrolyte synthesis strategy

Protonic ceramic fuel cells (PCFCs) are emerging as a promising technology for reduced temperature ceramic energy conversion devices. The BaCe 0.4 Zr 0.4 Y 0.1 Yb 0.1 O 3–δ (BCZYYb4411) electrolyte is notable for its high proton conductivity. However, the tendency of barium to volatilize in BCZYYb4411 during high-temperature sintering compromises its chemical stability and performance. This study investigates the effects of intentionally incorporating excess barium into BCZYYb4411, formulated as Ba 1+x Ce 0.4 Zr 0.4 Y0.1Yb 0.1 O 3–δ (where x = 0, 0.1, 0.2, and 0.3), with the aim of compensating barium evaporation and enhancing the physical and chemical properties. We find that excess barium results in a greater shrinkage rate, facilitating a denser electrolyte structure. This barium-enriched electrolyte demonstrates improved electrochemical performance by effectively counteracting the deleterious effects of barium evaporation. Applying this strategy to tubular PCFCs, we achieved a peak power density of 480 mW•cm –2 at 600 °C. This unique approach provides a simple, tunable, and easy-to-implement processing modification to achieve high-performance tubular PCFC.

25 ENERGY STORAGE↗

In Situ Nanoscale Dynamics Imaging in a Proton‐Conducting Solid Oxide for Protonic Ceramic Fuel Cells

Abstract Hydrogen fuel cells and electrolyzers operating below 600 °C, ideally below 400 °C, are essential components in the clean energy transition. Yttrium‐doped barium zirconate BaZr 0.8 Y 0.2 O 3‐d (BZY) has attracted a lot of attention as a proton‐conducting solid oxide for electrochemical devices due to its high chemical stability and proton conductivity in the desired temperature range. Grain interfaces and topological defects modulate bulk proton conductivity and hydration, especially at low temperatures. Therefore, understanding the nanoscale crystal structure dynamics in situ is crucial to achieving high proton transport, material stability, and extending the operating range of proton‐conducting solid oxides. Here, Bragg coherent X‐ray diffractive imaging is applied to investigate in situ and in 3D nanoscale dynamics in BZY during hydration over 40 h at 200 °C, in the low‐temperature range. An unexpected activity of topological defects and subsequent cracking is found on a nanoscale covered by the macroscale stability. The rearrangements in structure correlate with emergent regions of different lattice constants, suggesting heterogeneous hydration. The results highlight the extent and impact of nanoscale processes in proton‐conducting solid oxides, informing future development of low‐temperature protonic ceramic electrochemical cells.

25 ENERGY STORAGE↗

Machine Learning-Accelerated First-Principles Molecular Dynamics Explains Anomalous Lattice Thermal Expansion in BaZr 0.78 Y 0.22 O 3-δ

Fuel cells are a vital clean energy technology that converts chemical energy directly into electricity with high efficiency, making them a cornerstone of a sustainable energy future. Herein we investigate the thermal and chemical lattice expansion behavior of hydrated BaZr 0.78 Y 0.22 O 3-δ using machine learning-accelerated ab initio molecular dynamics simulations. Here, our results reproduce the experimentally observed non-monotonic and anomalous temperature dependence of lattice expansion, which we attribute to the competing effects of thermal expansion and dehydration—two mechanisms that influence the lattice expansion in opposite directions. The importance of this work lies in its detailed demonstration of how advanced computational techniques can accurately capture complex environmental effects, providing a valuable framework for modeling similar phenomena in a variety of material systems and applications.

Proton conducting fuel cell↗

Enhanced electrolysis performance through hierarchical nanoparticle formation in the BaCo 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 3-δ cathode materials system

This study demonstrated that the activity of a triple conducting BaCo 0.4 Fe 0.4 Zr 0.1 Y 0.1 O 3-δ (BCFZY0.1) air cathode was improved by in situ formation BCFZY0.1 nanoparticles (NPs). The NPs, directly formed from the reaction of BCFZY0.1 with H 2 O and CO 2 from air under electrolysis measurements conditions, were uniformly distributed in a porous BCFZY0.1 framework. At 600 °C, the current density increased and reached a plateau of 1.12 A/cm 2 with the hierarchical BCFZY0.1 cathode under electrolysis conditions within 400 h operation. Distribution of Relaxation Time (DRT) measurements found that the polarization resistance decreased over time as NPs were formed. Furthermore, SEM and TEM results confirm the nanoparticle formation, and the chemical and structural features were assigned to a BCFZY0.1 phase.

08 HYDROGEN↗