Protonic Ceramic Electrochemical Cells Research Articles

Y, Yb, and Gd tri-doping on B-site of Ba(Zr, Ce)O3-δ with improved proton conduction performance

Perovskite-type proton conducting electrolytes are garnering significant attention due to its key role in protonic ceramic electrochemical cells (PCEC) and its application in hydrogen sensors (HS) used for metal melt measurements. Developing high proton conduction perovskite materials with good chemical stability is always a worldwide research focus. In this paper, Y, Yb and Gd triple-doping on B-site of BaCeO3-BaZrO3 solid solution were carried out to investigate the effect of gadolinium doping on the performance of protonic conducting electrolytes. BaZr0.1Ce0.7(Y0.5Yb0.5)0.2-xGdxO3-δ (x = 0, 0.1, 0.15 and 0.2), which were also referred as BZCYYbGdx (x = 0, 10, 15 and 20), were synthesized by solid-state reaction at 1600 °C for 10 h. It is found that BZCYYbGd15 has the highest proton conductivity and proton transfer number among the four prepared materials. The proton mobility of BZCYYbGd15 is 4.06 × 10−6 cm2/(Vꞏs) at 800 °C, which increases with an increased temperature. Its proton transfer number is higher than 0.9 at 500 °C under the atmosphere of PH2O = 0.018 atm. A moderate doping of gadolinium increases the temperature threshold for proton conduction. Proton, oxygen vacancy, electron hole and total conductivity activation energies of BZCYYbGd15 under the wet atmosphere are found to be 0.74, 1.58, 1.41 and 0.92 eV, respectively. Furthermore, the chemical stability of pellets is improved after gadolinium doping. This study provides a reference value for future research on high proton conduction electrolytes.

Developing advanced oxygen electrodes for reversible protonic ceramic electrochemical cells via controlled bismuth doping on diverse perovskite lattice positions

The development of reversible protonic ceramic electrochemical cells (R-PCECs) is hampered by insufficient oxygen electrode activity. This study addresses this challenge by introducing bismuth (Bi) into different lattice sites (A-site, B-site, or both) of Ba(Co0.7Fe0.3)0.85Ta0.15O3-δ (BCFT) to develop novel oxygen electrode materials. Extensive characterizations and density functional theory calculations demonstrate that introducing Bi onto the B-site promotes oxygen vacancy formation and hydration, facilitates proton transportation and improves oxygen exchange ability, leading to the enhanced catalytic activity. In contrast, Bi on the A-site hinders performance. R-PCEC using Ba(Co0.7Fe0.3)0.75Bi0.10Ta0.15O3-δ (B-BCFT) oxygen electrode achieves exceptional performance in fuel cell (1.485 W cm−2 at 650 °C) and electrolysis modes (−1.839 A cm−2 at 1.4 V and 650 °C). Notably, B-BCFT demonstrates outstanding operational stability, lasting for 150 h in both modes and enduring 35 cycles of reversible operation. These results make B-BCFT a promising oxygen electrode material candidate for R-PCECs.

An efficient electrode for reversible oxygen reduction/evolution and ethylene electro-production on protonic ceramic electrochemical cells

Protonic ceramic electrochemical cells (PCECs) have demonstrated great promise for applications in the generation of electricity, and the synthesis of chemicals (for example, ethylene). However, enhancing the electrochemical reactions kinetics and stability of PCECs electrodes is one grand challenge. Here, we present a novel electrode material via a co-doping of cesium (Cs) and niobium (Nb) on PrBaCo2O6−δ with the composition of PrBa0.9Cs0.1Co1.9Nb0.1O6−δ (PBCCN), which naturally decomposes into dual phases of a double-perovskite PBCCN (DP-PBCCN, ∼92.3 wt%) and a single-perovskite Ba0.9Cs0.1Co0.95Nb0.05O3−δ (SP-BCCN, ∼7.7 wt%) under typical powder processing conditions. PBCCN exhibits a low area-specific resistance (ASR) value of 0.107 Ω cm2, an outstanding performance of 2.04 W cm−2 in fuel cell (FC) mode, a current density of −2.84 A cm−2 at 1.3 V in electrolysis cell (EC) mode, and promising reversible operational durability of 53 cycles in ∼212 h at +/− 0.5 A cm−2 and 650 °C. Cs doping generates more oxygen vacancies and accelerates the oxygen exchange kinetics, while Nb doping effectively enhances the stability, as illustrated by the analyses of X-ray photoelectron spectroscopy, and electrical conductivity relaxations. When applied as the positrode for electrochemical non-oxidative dehydrogenation of ethane (C2H6) to ethylene (C2H4) on PCECs, it displays an encouraging C2H6 conversion of 12.75% and a C2H4 selectivity of 98.4% at 1.2 V.

Surface-doped perovskite electrolyte for low-temperature ceramic electrochemical cells

Protonic ceramic electrochemical cells (PCECs) can be employed for power generation and sustainable hydrogen production. Lowering the PCEC operating temperature to >500 °C can facilitate its scale-up and commercialization. However, achieving high energy efficiency and long-term durability at low operating temperatures is a long-standing challenge. Here, we report a simple and scalable approach for fabricating metal ion doping into perovskite (Li-doped SrTiO3 (STO)) using the sol-gel approach and presented as a proton conducting electrolyte with lower ohmic and polarization resistance for low-temperature ceramic fuel cells. The prepared electrolyte with symmetrical electrodes attains high power densities in fuel-cell mode (∼0.65 W cm−2 at 520 °C and ∼0.20 W cm−2 at 420 °C) and exceptional current densities in steam electrolysis mode (−0.94 A cm−2 at 1.4 V and 520 °C). Additionally, five-layer devices (Ni-NCAL/BCZYYb/Li-STO/BCZYYb/NCAL-Ni) demonstrate the proton fuel cell performance of 0.55 W cm−2 at 520 °C.

An Efficient Trifunctional Spinel-Based Electrode for Oxygen Reduction/Evolution Reactions and Nonoxidative Ethane Dehydrogenation on Protonic Ceramic Electrochemical Cells.

Protonic ceramic electrochemical cells (PCECs) have received considerable attention as they can directly generate electricity and/or produce chemicals. Development of the electrodes with the trifunctionalities of oxygen reduction/evolution and nonoxidative ethane dehydrogenation is yet challenging. Here these findings are reported in the design of trifunctional electrodes for PCECs with a detailed composition of Mn0.9Cs0.1Co2O4-δ (MCCO) and Co3O4 (CO) (MCCO-CO, 8:2 mass ratio). At 600°C, the MCCO-CO electrode exhibits a low area-specific resistance of 0.382 Ω cm2 and reasonable stability for ≈105h with no obvious degradation. The single cell with the MCCO-CO electrode shows an encouraging peak power density of 1.73W cm-2 in the fuel cell (FC) mode and a current density of -3.93 A cm-2 at 1.3V in the electrolysis cell (EC) mode at 700°C. Moreover, the MCCO-CO cell displays promising operational stability in FC mode (223h), EC mode (209h), and reversible cycling stability (52 cycles, 208h) at 650°C. The MCCO-CO single cell shows an encouraging ethaneconversion to ethylene (with a conversion of 40.3% and selectivity of 94%) and excellent H2 production rates of 4.65mL min-1 cm-2 at 1.5V and 700°C, respectively, with reasonable Faradaic efficiencies.

(Invited) Novel High Entropy Perovskite Oxides for High-Performance Protonic Ceramic Electrochemical Cells

Due to the intermediate operating temperatures (400-600oC), protonic ceramic electrochemical cells have attracted significant attention in the last 10 years because of the demonstration of potential applications of fuel-flexible fuel cells, water electrolysis to produce hydrogen, solid-state ammonia synthesis, electrochemical reduction of carbon dioxide to fuels, and fuel processing (e.g., natural gas to liquids). In addition to developing specific fuel electrodes for different electrocatalytic reactions, we need to discover new electrolyte and oxygen electrode materials generically for all the protonic ceramic electrochemical cells to further decrease the operating temperatures, increase performance, and prolong the long-term stability. The recently emerging materials of high entropy perovskite oxides have been reported to be able to serve as promising electrolyte and oxygen electrode materials. In this talk, we will summarize what Clemson University has done about developing, characterizing, understanding, and demonstrating high entropy perovskite oxides as high-performance and stable electrolyte and oxygen electrode materials for protonic ceramic electrochemical cells.

Electrocatalytic Upgrading of CO2 to Light Olefins in Protonic Ceramic Electrochemical Cells

Light olefins (ethylene, propylene, butylene) are primary building blocks for chemical manufacturing of large volume products including organic chemicals, plastics, and even sustainable aviation fuels. Currently, the dominant commercial process for olefin production is steam cracking of naphtha or ethane, which is highly energy intensive and accounts for a large fraction of global CO2 emissions. To decarbonize olefin production processes, electrochemical CO2-to-olefin conversion coupled with renewable or low-emission energy sources including electricity and heat offers an attractive alternative. Previously, extensive research efforts have been devoted to low temperature electrochemical CO2 reduction in aqueous media, i.e., occurring below 100 °C. This approach, however, still faces enormous scientific and technological challenges in improving CO2 utilization, energy efficiency, and product selectivity. In this work, we have developed a new electrochemical process for direct conversion of CO2 to ethylene at intermediate temperatures (350-500°C) in an electrochemical membrane reactor. This process is based on high-performance protonic ceramic electrochemical cells (PCECs) that integrate CO2 hydrogenation reaction to produce olefins in the cathode and concurrent hydrogen generation reaction in the anode to provide hydrogen for CO2 conversion. Highly active and selective catalysts for CO2-to-olefin conversion have been identified and integrated into the PCECs. Both the catalytic and electrochemical performances of the integrated reactor system are evaluated and optimized. In contrast to the use of molecular H2 in conventional thermal catalytic pathways, the active hydrogen in PCECs could be sourced from different feedstocks including H2O, light alkanes, and ammonia, etc. This work also provides valuable insights into the selection and design of efficient catalysts for electrochemical CO2 conversion at elevated temperatures.

Characterization of Proton Exchange in Protonic Ceramic Electrochemical Cells Using Operando Drifts

The protonic ceramic electrochemical cells (PCECs) have attracted tremendous attention for their fast hydrogen production at intermediate temperatures. This work applied in situ Diffuse reflectance infrared Fourier transform infrared spectroscopy (DRIFTS) together with electrochemical impedance spectroscopy (EIS), to characterizes transport and hydration properties of the state-of-the-art electrolyte materials. The adsorption of water molecules and formation of surface hydroxyl groups on the electrolyte surface as a function of temperature, steam concentration, and electrical potential were systematically investigated by DRIFTS under operando conditions. The quantitative information on the concentration of hydroxyl species on the electrolyte materials before and after exposure to steam were obtained. The determination of OH intensity leads to the direct determination of the proton exchange coefficient k, at different steam concentrations and biases. The results are unique and should be able to provide valuable insights into the mechanisms of proton formation, migration, and evolution under various operating conditions, which is critical to design better electrolyte compositions and optimize the operation conditions for next-generation PCECs.

(Invited) Protonic Ceramic Electrochemical Cells for Hydrogen Production and Sustainable Chemicals Synthesis

Protonic ceramic electrochemical cells (PCECs) are emerging as a promising technology for synthesizing chemicals with enhanced efficiency and sustainability. They exhibit versatility by efficiently synthesizing a wide range of chemicals using earth-abundant feedstocks such as H2O, N2, and CO2, while also contributing to the reduction of carbon footprint and improvement in energy efficiency during the upgrading of natural gas (methane). PCECs offer several notable advantages that set them apart from other chemical production technologies. One key advantage is their intermediate operating temperature range (300–600 °C), which thermodynamically and kinetically favors electrode chemistry. This temperature range also holds the potential for the simultaneous utilization of waste heat. In this presentation, we will highlight our recent achievements in utilizing PCECs for CO2 conversion and utilization, methane valorization, and hydrogen production.

Protonic Ceramic Electrochemical Cell Manufacturing at Idaho National Laboratory

Protonic Ceramic Electrochemical Cells (PCECs), operating at intermediate temperatures of 400-600oC, show great potential for hydrogen production and versatile chemical manufacturing. As this technology rapidly evolves, scaling up production in both quantity and size is crucial. This step bridges the gap between fundamental academic research on small button cells (e.g., 10 mm to 1 inch) and higher-technology readiness level development of industry-standard units (> 10x10 cm2) for stack assembly. At Idaho National Laboratory, we've made significant strides in this transition by applying advanced manufacturing technologies and our expertise in materials science and engineering. Our approach integrates materials, structural, and interface engineering research and development into the cell fabrication process, guided by a stringent quality assurance and quality control (QA&QC) system. This ensures the reliable, repeatable, and durable performance of PCECs.

(Invited) Streamlined Production of Protonic Ceramic Electrochemical Cells Via Ultrasonic Spray Coating

Thin solid oxide films are crucial for developing high-performance solid oxide-based electrochemical devices aimed at decarbonizing the global energy system. This presentation introduces ultrasonic spray coating technique (USC) for producing <10 µm thin electrolyte films, as well as uniform 4×4 cm2 oxygen electrode films, with a systematic process optimization considering solid loading rates, spray passes, and annealing temperature etc. Notably, the integrated approach highlights the versatility of USC in addressing both oxygen electrode and electrolyte fabrication challenges. The resulting protonic ceramic electrochemical cells, fabricated with these optimized parameters, exhibit remarkable electrochemical performance, structural integrity, and stability in both fuel cell and electrolysis modes. This presentation provides a holistic perspective on scalable production techniques, showcasing the potential of ultrasonic spray coating for advancing large-sized solid oxide electrochemical cells.

Enhanced Electrochemical Performance of Double Perovskites as Cathodes in Reversible Ceramic Electrochemical Cells through Nb Doping

Efficient and cost-effective generation of electricity and hydrogen holds promise through reversible protonic ceramic electrochemical cells (R-PCECs). However, the successful commercialization of R-PCECs depends on the advancement of air electrodes that are both highly active and durable. Here, we made an air electrode material with two phases of double perovskite and single perovskite by doping Nb into B-site of the traditional PrBaCo2O6 double perovskite. The coexistence of the mixed double perovskite and single perovskite phases demonstrates superior electrochemical performance and durability compared to pristine double perovskite and single perovskite materials when employed as cathode materials. X-ray photoelectron spectroscopy (XPS), synchrotron radiation X-ray absorption spectroscopy (XAS) and neutron diffraction analysis reveal that this enhancement is primarily attributed to the introduction of high-valence Nb5+, resulting in an increased number of oxygen vacancies and structural stability. The findings presented in this study contribute valuable insights into the design and development of advanced cathode materials for solid oxide fuel cells and electrolyzers, with the potential for applications in sustainable energy conversion and storage technologies.

Surface reconstruction of a perovskite air electrode boosts the activity and durability of reversible protonic ceramic electrochemical cells

Reversible protonic ceramic electrochemical cells (R-PCECs) display a vast range of potential applications as an efficient and low-cost technology for the generation of electricity and the production of high-value-added chemicals. However, electrode surface reaction kinetics, especially the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), pose significant challenges to the development of R-PCECs. To achieve the commercialization of R-PCECs, the key lies in the development of an air electrode that possesses both high activity and durability. In this study, a perovskite oxide electrode composed of Pr0.5Sr0.5Co0.9Nb0.1O3-δ (PSCN) is designed as a novel air electrode for R-PCECs. During operation, nanoparticles (NPs) with a formula SrCo0.5Nb0.5O3-δ (SCN) are in situ generated on the PSCN framework, thus forming an SCN-coated PSCN (SCN–PSCN) composite with abundant interfaces. These NPs and interfaces notably boost the activity of the composite electrode. As the air electrode for R-PCECs, the SCN–PSCN electrode exhibits excellent performance at 600 °C, in dual modes of fuel cell and electrolysis cell. It achieves a peak power density of 0.89 W cm−2 and a current density of 1.27 A cm−2 at 1.3V. Also, the SCN–PSCN air electrode demonstrates stability exceeding 100 h in both FC and EC modes.

Electrochemical behaviour of redox-robust electrode in contact with protonic electrolyte: Case of double-layered Sr2Fe1.5Mo0.5O6-δ - Ce0.8Sm0.2O2-δ composite

Electrochemical devices based on proton-conducting oxides offer a significant potential for implementation in a variety of high-temperature electrochemical applications. It is a well-known fact that electrochemical devices require active electrodes to function optimally. Over the last few years, Sr2Fe1.5Mo0.5O6-δ has received much attention as an effective redox-robust electrode for oxygen conducting electrolytes. This study presents, for the first time, the results of investigations on a double-layered composite electrode based on Sr2Fe1.5Mo0.5O6-δ in contact with a barium-free proton-conducting electrolyte La0.9Sr0.1ScO3-δ. It was found that the investigated electrode exhibits low polarization resistance about 0.15 and 0.22 Ohm cm2 in wet air and wet hydrogen at 600 °C, respectively. In addition, the electrode exhibits acceptable redox stability and CO2 tolerance. Also, the results of electrochemical impedance spectra analysis and a discussion on the parallel pathways of hydrogen oxidation and oxygen reduction reactions and the nature of rate-determining steps are presented in the manuscript. The obtained results show the high prospects for a Sr2Fe1.5Mo0.5O6-δ - based composite electrode for protonic ceramic electrochemical cells.

Efficient Energy Storage via Methane Production Using Protonic Ceramic Electrochemical Cells

Protonic ceramic electrochemical cells (PCECs) are promising energy storage technologies due to their high performance and ability to convert CO2 into value-added chemicals. However, there are many fundamental aspects of this technology that require investigation to better understand its interactions and opportunities. Thus, this paper focuses on the development of a steady-state PCEC model, encompassing intricate details of reactive porous-media transport, elementary catalytic chemistry, and electrochemistry within unit cells. The model is calibrated and validated using experimental data. The model presents the rate of methane production at different temperatures and revealed that efficient PCEC for co-electrolysis of CO2 and H2O is operated in the temperature range of 420–470 °C and the optimum being 450 °C at the rate of 0.0391 moldm−3 min−1. It provides insights into the effects of overpotentials on cell performance. At a current density of 3000 A/m2 the ohmic, concentration, and activation overpotentials amount to 0.65, 0.004, and 0.19 V, respectively. The results obtained from the model highlight the potential of PCECs as efficient CO2 sinks for decarbonization purposes and as a means of methane production. Furthermore, the model's findings offer valuable guidance for the design, selection of stacks, and choice of building materials in PCEC systems. The potential applications of PCECs as real-life fuel utilization technologies are justified with improved material development to reduce cell overpotentials, opening doors for scale-up and eventual commercialization. These findings contribute to the development of sustainable energy systems and advance the pursuit of decarbonization goals.

Synergistic Bulk and Surface Engineering for Expeditious and Durable Reversible Protonic Ceramic Electrochemical Cells Air Electrode.

Reversible protonic ceramic electrochemical cells (R-PCECs) offer the potential for high-efficiency power generation and green hydrogen production at intermediate temperatures. However, the commercial viability of R-PCECs is hampered by the sluggish kinetics of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) within conventional air electrodes operating at reduced temperatures. To address this challenge, this work introduces a novel approach based on the simultaneous optimization of bulk-phase metal-oxygen bonds and in-situ formation of a metal oxide nano-catalyst surface modification. This strategy is designed to expedite the ORR/OER electrocatalytic activity of air electrodes exhibiting triple (O2-, H+, e-) conductivity. Specifically, this engineered air electrode nanocomposite-Ba(Co0.4Fe0.4Zr0.1Y0.1)0.95Ni0.05F0.1O2.9-δ demonstrates remarkable ORR/OER catalytic activity and exceptional durability in R-PCECs. This is evidenced by significantly improved peak power density from 626 to 996mW cm-2 and highly stable reversibility over a 100-h cycling period. This research offers a rational design strategy to achieve high-performance R-PCEC air electrodes with superior operational activity and stability for efficient and sustainable energy conversion and storage.

“Template-assisted synthesis” strategy to improve the bifunctional catalytic activity of oxygen electrode for reversible protonic ceramic electrochemical cell

Reversible protonic ceramic electrochemical cell (R-PCEC) is a new energy conversion device that can achieve efficient conversion between chemical energy and electrical energy. However, the oxygen electrode has poor activity towards oxygen evolution reaction (OER) and oxygen reduction reaction (ORR), which hinders the large-scale application of R-PCEC. Therefore, in order to improve the catalytic activity of oxygen electrodes, La0.5Sr0.5Co0.2Fe0.8O3 (LSCF) is prepared using mesoporous silica SiO2 (SBA-15) and polymethyl methacrylate (PMMA) as templates, and it was combined with BaZr0.1Ce0.7Y0.2O3-δ (BZCY) to form a composite oxygen electrode for R-PCEC. Compared to the LSCF with solid-state reaction method, LSCF with hard-template method shows higher specific surface area and more oxygen vacancy, resulting in excellent ORR catalytic activity. In addition, LSCF prepared using PMMA as a template exhibits the best ORR catalytic activity, and the single cell with this composite oxygen electrode shows the highest maximum power density of 406 mW cm−2 in fuel cell (FC) mode with wet H2 (3%H2O) and air as the fuel and oxidant, respectively. Additionally, it demonstrates a current density of −973 mA cm−2 at 1.3 V in electrolysis cell (EC) mode with wet air (10%H2O) as the oxidant. The single cell also shows good reversibility in FC mode and EC mode. This work provides a new strategy to improve the bifunctional activity of oxygen electrode in R-PCEC.

Performance improvement of oxygen electrode in reversible protonic ceramic electrochemical cell by co-doping of La and F

Reversible protonic ceramic electrochemical cell (R-PCEC) has demonstrated high potential as an energy storage and conversion device. Efforts have primarily concentrated on the development of oxygen electrodes being to increase their performance and reduce performance degradation. In this work, three perovskite materials, namely Ba0.9Co0.2Fe0.7Nb0.1O3-δ (BCFN), Ba0.8La0.1Co0.2Fe0.7Nb0.1O3-δ (BLCFN), and Ba0.8La0.1Co0.2Fe0.7Nb0.1F0.1O2.9-δ (BLCFNF) are investigated. Both doping with La and co-doping with La and F lead to a notable reduction in the average valence states of Fe, Co, and Nb elements, further resulting in an increase in oxygen vacancy concentration, thereby enhancing the oxygen migration ability of the material. The H2O partial pressure does not have a significant impact on the polarization resistance (Rp) of the oxygen electrode. Conversely, the rise in Rp is highly correlated with the decrease in oxygen partial pressure, suggesting that the primary factor influencing the reaction rate of the oxygen electrode process is the exchange of oxygen ions on the surface of the electrode. BLCFNF exhibits the best oxygen migration and surface exchange ability, resulting in the lowest Rp. When BLCFNF was used as the oxygen electrode in a R-PCEC with the humidity air (10%H2O) and humidified H2 (3%H2O) as oxidant and fuel, respectively, it exhibits the highest maximum power density of 472 mW cm−2, and a current density of −682.6 mA cm−2 (1.3 V) at 650 °C. In addition, BLCFNF also shows good durability in both discharge and electrolysis process. The results indicate that La and F co-doped BLCFNF material is a promising oxygen electrode material for R-PCECs.

Transport properties of highly dense proton-conducting BaSn1−xInxO3−δ ceramics

Doped barium stannate belongs to the perovskite-structured complex oxides with proton transport capability. Such objects are of high interest in terms of their application in various protonic ceramic electrochemical cells. In the present work, In-doped barium stannate (BaSn1−xInxO3−δ, 0 ≤ x ≤ 0.4) materials were prepared and thoroughly characterized by structural, microstructural, and electrochemical techniques. The single-phase and high-dense ceramic materials were prepared by the conventional solid-state synthesis route over the entire doping range investigated. The chemical composition of these materials was found to be in close agreement with the nominal values, indicating no evaporation of Ba-, Sn-, or In-containing phases during sintering. The high-temperature electrochemical analysis showed that the ionic conductivity of BaSn1−xInxO3−δ gradually increases with increasing the In-content without reaching a concentration maximum, even for high dopant concentrations. The relatively high activation energy values indicate that this ionic conductivity is determined by oxygen-ionic transport, which, however, becomes predominantly protonic at reduced temperatures. The determination of bulk and grain boundary transport showed that both were improved with the In-doping. The possible reasons for these observations were discussed in detail in this work. Therefore, the obtained data are important for discovering the transport properties of stannates and their potential applications.

Highly efficient La/Ni co-doped strontium titanate catalyst for co-production of propylene and hydrogen from propane in protonic ceramic electrochemical cells

A highly efficient La/Ni co-doped strontium titanate (LSNT) perovskite catalyst is developed and integrated in a protonic ceramic electrochemical cell for co-production of propylene and high-purity hydrogen from commercial propane feedstock. Propane conversion and hydrogen production rate can be effectively enhanced under an applied current due to the electrochemical promotion effect and/or shifted reaction equilibrium induced by rapid separation of hydrogen product. Water vapor in the feed gas could significantly improve the catalyst stability by suppressing the coke formation. The propane conversion could reach up to 53% at 600 °C under a current density of 90 mA cm−2. The LSNT catalyst also shows excellent tolerance for the sulfur contaminant in commercial propane gas. The excellent performance of the LSNT catalyst is attributed to the highly active and selective Ni species at the interface with the perovskite substrate, which are formed in situ via reduction-induced exsolution under reaction conditions.