A High-Strength Solid Oxide Fuel Cell Supported by an Ordered Porous Cathode Membrane.

The phase inversion tape casting has been widely used to fabricate open straight porous supports for solid oxide fuel cells (SOFCs), which can offer better gas transmission and minimize the concentration polarization. However, the overall weak strength of the macro-porous structure still limits the applications of these SOFCs. In this work, a novel SOFC supported by an ordered porous cathode membrane with a four-layer configuration containing a finger-like porous 3 mol% yttria- stabilized zirconia (3YSZ)-La0.8Sr0.2Co0.6Fe0.4O3-δ (LSCF) catalyst, porous 8 mol% yttria-stabilized zirconia (8YSZ)-LSCF catalyst, and dense 8YSZ porous 8YSZ-NiO catalyst is successfully prepared by the phase inversion tape casting, dip-coating, co-sintering, and impregnation process. The flexural strength of the open straight porous 3YSZ membrane is as high as 131.95 MPa, which meets the requirement for SOFCs. The cathode-supported single cell shows a peak power density of 540 mW cm-2 at 850 °C using H2 as the fuel. The degradation mechanism of the SOFC is investigated by the combination of microstructure characterization and distribution of relaxation times (DRT) analysis.

Harnessing High-Throughput Computational Methods to Accelerate the Discovery of Optimal Proton Conductors for High-Performance and Durable Protonic Ceramic Electrochemical Cells.

The pursuit of high-performance and long-lasting protonic ceramic electrochemical cells (PCECs) is impeded by the lack of efficient and enduring proton conductors. Conventional research approaches, predominantly based on a trial-and-error methodology, have proven to be demanding of resources and time-consuming. Here, this work reports the findings in harnessing high-throughput computational methods to expedite the discovery of optimal electrolytes for PCECs. This work methodically computes the oxygen vacancy formation energy (EV), hydration energy (EH), and the adsorption energies of H2O and CO2 for a set of 932 oxide candidates. Notably, these findings highlight BaSnxCe0.8-xYb0.2O3-δ (BSCYb) as a prospective game-changing contender, displaying superior proton conductivity and chemical resilience when compared to the well-regarded BaZrxCe0.8-xY0.1Yb0.1O3-δ (BZCYYb) series. Experimental validations substantiate the computational predictions; PCECs incorporating BSCYb as the electrolyte achieved extraordinary peak power densities in the fuel cell mode (0.52 and 1.57 W cm-2 at 450 and 600 °C, respectively), a current density of 2.62 A cm-2 at 1.3 V and 600 °C in the electrolysis mode while demonstrating exceptional durability for over 1000-h when exposed to 50% H2O. This research underscores the transformative potential of high-throughput computational techniques in advancing the field of proton-conducting oxides for sustainable power generation and hydrogen production.

A Synergistic Three-Phase, Triple-Conducting Air Electrode for Reversible Proton-Conducting Solid Oxide Cells.

Reversible proton-conducting solid oxide cells (R-PSOCs) have the potential to be the most efficient and cost-effective electrochemical device for energy storage and conversion. A breakthrough in air electrode material development is vital to minimizing the energy loss and degradation of R-PSOCs. Here we report a class of triple-conducting air electrode materials by judiciously doping transition- and rare-earth metal ions into a proton-conducting electrolyte material, which demonstrate outstanding activity and durability for R-PSOC applications. The optimized composition Ba0.9Pr0.1Hf0.1Y0.1Co0.8O3-δ (BPHYC) consists of three phases, which have a synergistic effect on enhancing the performance, as revealed from electrochemical analysis and theoretical calculations. When applied to R-PSOCs operated at 600 °C, a peak power density of 1.37 W cm-2 is demonstrated in the fuel cell mode, and a current density of 2.40 A cm-2 is achieved at a cell voltage of 1.3 V in the water electrolysis mode under stable operation for hundreds of hours.

Self-hydrating of a ceria-based catalyst enables efficient operation of solid oxide fuel cells on liquid fuels.

The commercialization of solid oxide fuel cells (SOFCs) that run on liquid hydrocarbon fuels is hindered by the poor coking tolerance of the state-of-the-art anode. Among the strategies developed, modulating the reforming reaction site's local steam/carbon ratios to enhance the coking tolerance is efficient but challenging. Here we report our rational design of a ceria-based catalyst (with a nominal composition of Ce0.95Ru0.05O2-δ, CR5O) that demonstrates remarkable tolerance to coking while maintaining excellent activity for direct utilization of liquid fuels in SOFCs. Under operating conditions, the catalyst is transformed to a partially reduced oxide frame covered with Ru nanoparticles (Ru/Ce0.95Ru0.05-xO2-δ, Ru/CR5-xO), as confirmed by experimental analyses. The Ru/CR5-xO demonstrates excellent self-hydration capability to remove the coke. When applied to the Ni-yttria-stabilized zirconia (Ni-YSZ) anode of an SOFC with liquid fuels, the catalyst enables excellent performance, achieving a peak power density of 1.010 W cm-2 without coking for ∼200 h operation (on methanol) at 750 °C. Furthermore, density functional theory calculations reveal that the high activity and coking tolerance of the Ru/CR5-xO catalyst-coated Ni-YSZ anode is attributed to the reduced energy barrier for the rate-limiting step and the formation of a COH intermediate for rapid carbon removal.

Self-Construction of Efficient Interfaces Ensures High-Performance Direct Ammonia Protonic Ceramic Fuel Cells.

Direct ammonia protonic ceramic fuel cells (PCFCs) are highly efficient energy conversion devices since ammonia as a carbon-neutral hydrogen-rich carrier shows great potential for storage and long-distance transportation when compared with hydrogen fuel. However, traditional Ni-based anodes readily suffer from severe structural destruction and dramatic deactivation after long-time exposure to ammonia. Here a Sr2 Fe1.35 Mo0.45 Cu0.2 O6-δ (SFMC) anode catalytic layer (ACL) painted onto a Ni-BaZr0.1 Ce0.7 Y0.1 Yb0.1 O3- δ (BZCYYb) anode with enhanced catalytic activity and durability toward the direct utilization of ammonia is reported. A tubular Ni-BZCYYb anode-supported cells with the SFMC ACL show excellent peak power densities of 1.77 W cm-2 in wet H2 (3% H2 O) and 1.02 W cm-2 in NH3 at 650 °C. A relatively stable operation of the cells is obtained at 650 °C for 200 h in ammonia fuel. Such achieved improvements in the activity and durability are attributed to the self-constructed interfaces with the phases of NiCu or/and NiFe for efficient NH3 decomposition, resulting in a strong NH3 adsorption strength of the SFMC, as confirmed by NH3 thermal conversion and NH3 -temperature programmed desorption. This research offers a valuable strategy of applying an internal catalytic layer for highly active and durable ammonia PCFCs.

Durable and High-Performance Thin-Film BHYb-Coated BZCYYb Bilayer Electrolytes for Proton-Conducting Reversible Solid Oxide Cells.

Proton-conducting reversible solid oxide cells are a promising technology for efficient conversion between electricity and chemical fuels, making them well-suited for the deployment of renewable energies and load leveling. However, state-of-the-art proton conductors are limited by an inherent trade-off between conductivity and stability. The bilayer electrolyte design bypasses this limitation by combining a highly conductive electrolyte backbone (e.g., BaZr0.1Ce0.7Y0.1Yb0.1O3-δ (BZCYYb1711)) with a highly stable protection layer (e.g., BaHf0.8Yb0.2O3-δ (BHYb82)). Here, a BHYb82-BZCYYb1711 bilayer electrolyte is developed, which dramatically enhances the chemical stability while maintaining high electrochemical performance. The dense and epitaxial BHYb82 protection layer effectively protects the BZCYYb1711 from degradation in contaminating atmospheres such as high concentrations of steam and CO2. When exposed to CO2 (3% H2O), the bilayer cell degrades at a rate of 0.4 to 1.1%/1000 h, which is much lower than the unmodified cells at 5.1 to 7.0%. The optimized BHYb82 thin-film coating adds negligible resistance to the BZCYYb1711 electrolyte while providing a greatly enhanced chemical stability. Bilayer-based single cells demonstrated state-of-the-art electrochemical performance, with a high peak power density of 1.22 W cm-2 in the fuel cell mode and -1.86 A cm-2 at 1.3 V in the electrolysis mode at 600 °C, while demonstrating excellent long-term stability.

Single-Phase Ternary Compounds with a Disordered Lattice and Liquid Metal Phase for High-Performance Li-Ion Battery Anodes.

Si is considered as the promising anode materials for lithium-ion batteries (LIBs) owing to their high capacities of 4200 mAh g-1 and natural abundancy. However, severe electrode pulverization and poor electronic and Li-ionic conductivities hinder their practical applications. To resolve the afore-mentioned problems, we first demonstrate a cation-mixed disordered lattice and unique Li storage mechanism of single-phase ternary GaSiP2 compound, where the liquid metallic Ga and highly reactive P are incorporated into Si through a ball milling method. As confirmed by experimental and theoretical analyses, the introduced Ga and P enables to achieve the stronger resistance against volume variation and metallic conductivity, respectively, while the cation-mixed lattice provides the faster Li-ionic diffusion capability than those of the parent GaP and Si phases. The resulting GaSiP2 electrodes delivered the high specific capacity of 1615 mAh g-1 and high initial Coulombic efficiency of 91%, while the graphite-modified GaSiP2 (GaSiP2@C) achieved 83% of capacity retention after 900 cycles and high-rate capacity of 800 at 10,000 mA g-1. Furthermore, the LiNi0.8Co0.1Mn0.1O2//GaSiP2@C full cells achieved the high specific capacity of 1049 mAh g-1 after 100 cycles, paving a way for the rational design of high-performance LIB anode materials.

An Efficient High-Entropy Perovskite-Type Air Electrode for Reversible Oxygen Reduction and Water Splitting in Protonic Ceramic Cells.

Reversible protonic ceramic electrochemical cells (R-PCECs) are emerging as ideal devices for highly efficient energy conversion (generating electricity) and storage (producing H2 ) at intermediate temperatures (400-700 °C). However, their commercialization is largely hindered by the development of highly efficient air electrodes for oxygen reduction and water-splitting reactions. Here, the findings in the design of a highly active and durable air electrode are reported: high-entropy Pr0.2 Ba0.2 Sr0.2 La0.2 Ca0.2 CoO3- δ (HE-PBSLCC), which exhibits impressive activity and stability for oxygen reduction and water-splitting reactions, as confirmed by electrochemical characterizations and structural analysis. When used as an air electrode of R-PCEC, the HE-PBSLCC achieves encouraging performances in dual modes of fuel cells (FCs) and electrolysis cells (ECs) at 650 °C, demonstrating a maximum power density of 1.51 W cm-2 in FC mode, and a current density of -2.68 A cm-2 at 1.3 V in EC mode. Furthermore, the cells display good operational durabilities in FC and EC modes for over 270 and 500 h, respectively, and promising cycling durability for 70 h with reasonable Faradaic efficiencies. This study offers an effective strategy for the design of active and durable air electrodes for efficient oxygen reduction and water splitting.

A New Class of Proton Conductors with Dramatically Enhanced Stability and High Conductivity for Reversible Solid Oxide Cells.

Reversible solid oxide cells based on proton conductors (P-ReSOCs) have potential to be the most efficient and low-cost option for large-scale energy storage and power generation, holding promise as an enabler for the implementation of intermittent renewable energy technologies and the widespread utilization of hydrogen. Here, the rational design of a new class of hexavalent Mo/W-doped proton-conducting electrolytes with excellent durability while maintaining high conductivity is reported. Specifically, BaMo(W)0.03 Ce0.71 Yb0.26 O3-δ exhibits dramatically enhanced chemical stability against high concentrations of steam and carbon dioxide than the state-of-the-art electrolyte materials while retaining similar ionic conductivity. In addition, P-ReSOCs based on BaW0.03 Ce0.71 Yb0.26 O3-δ demonstrate high peak power densities of 1.54, 1.03, 0.72, and 0.48 W cm-2 at 650, 600, 550, and 500 °C, respectively, in the fuel cell mode. During steam electrolysis, a high current density of 2.28 A cm-2 is achieved at a cell voltage of 1.3 V at 600 °C, and the electrolysis cell can operate stably with no noticeable degradation when exposed to high humidity of 30% H2 O at -0.5 A cm-2 and 600 °C for over 300 h. Overall, this work demonstrates the promise of donor doping for obtaining proton conductors with both high conductivity and chemical stability for P-ReSOCs.

Surface restructuring of a perovskite-type air electrode for reversible protonic ceramic electrochemical cells.

Reversible protonic ceramic electrochemical cells (R-PCECs) are ideally suited for efficient energy storage and conversion; however, one of the limiting factors to high performance is the poor stability and insufficient electrocatalytic activity for oxygen reduction and evolution of the air electrode exposed to the high concentration of steam. Here we report our findings in enhancing the electrochemical activity and durability of a perovskite-type air electrode, Ba0.9Co0.7Fe0.2Nb0.1O3-δ (BCFN), via a water-promoted surface restructuring process. Under properly-controlled operating conditions, the BCFN electrode is naturally restructured to an Nb-rich BCFN electrode covered with Nb-deficient BCFN nanoparticles. When used as the air electrode for a fuel-electrode-supported R-PCEC, good performances are demonstrated at 650 °C, achieving a peak power density of 1.70 W cm-2 in the fuel cell mode and a current density of 2.8 A cm-2 at 1.3 V in the electrolysis mode while maintaining reasonable Faradaic efficiencies and promising durability.

High-Performance, Thermal Cycling Stable, Coking-Tolerant Solid Oxide Fuel Cells with Nanostructured Electrodes.

Solid oxide fuel cells (SOFCs) are a promising solution to a sustainable energy future. However, cell performance and stability remain a challenge. Durable, nanostructured electrodes fabricated via a simple, cost-effective method are an effective way to address these problems. In this work, both the nanostructured PrBa0.5Sr0.5Co1.5Fe0.5O5+δ (PBSCF) cathode and Ni-Ce0.8Sm0.2O1.9 (SDC) anode are fabricated on a porous yttria-stabilized zirconia (YSZ) backbone via solution infiltration. Symmetrical cells with a configuration of PBSCF|YSZ|PBSCF show a low interfacial polarization resistance of 0.03 Ω cm2 with minimal degradation at 700 °C for 600 h. Ni-SDC|YSZ|PBSCF single cells exhibit a peak power density of 0.62 W cm-2 at 650 °C operated on H2 with good thermal cycling stability for 110 h. Single cells also show excellent coking tolerance with stable operation on CH4 for over 120 h. This work offers a promising pathway toward the development of high-performance and durable SOFCs to be powered by natural gas.

Critical Role of Anion Donicity in Li2S Deposition and Sulfur Utilization in Li-S Batteries.

Lithium-sulfur batteries offer a high theoretical gravimetric energy density and low cost, but the full utilization of the sulfur electrode has been limited by the premature passivation of insulating lithium sulfide (Li2S). Anion has been one of the major parameters to improve Li-S batteries in addition to solvent, additives, and electrode structures. Here, we reveal the role of anion donicity on the passivation of Li-S battery and its underlying working mechanism. We show that anions with high donicity effectively reduce the charge-transfer resistance during the cycling of Li-S cells and alleviate the Li2S passivation by transforming the dense film Li2S to porous three-dimensional flake Li2S. UV-vis spectroscopy revealed that anions with higher donicity exhibit higher Li2S4 solubility, which is consistent with their stronger bonding to Li+, as revealed by nuclear magnetic resonance and density functional theory calculations. Our study reveals the role of anion donicity in Li2S passivation and its underlying mechanism, offering rational design consideration for electrolyte salts in achieving high sulfur utilization and high energy efficiency for Li-S batteries.