Surface Chemistry Modulation of BaGd0.8La0.2Co2O6-δ As Active Air Electrode for Solid Oxide Cells.

Modulation of the surface chemistry of air electrodes makes it possible to significantly improve the electrocatalytic performance of solid oxide cells (SOCs). Here, the surface chemistry of BaGd0.8La0.2Co2O6-δ (BGLC) double perovskite is modulated by treatment in an acidic citric acid solution. The treatment leads to corrosion on the surface of BGLC particles, and the effect is dependent on the acidity of the solution. As the acidity of solution is low, Ba cations are selectively dissolved out of the BGLC surface, while as the acidity increases, the corrosion becomes more homogeneous. The Ba surface deficiency remarkably increases the concentration of surface oxygen vacancies and electrocatalytic activity of BGLC. To avoid the loss of Ba-deficient surface during the conventional high temperature sintering process, a sintering-free fabrication route is utilized to directly assemble the Ba-deficient BGLC powder into an air electrode. A single cell with the surface Ba-deficient BGLC electrode shows a peak power density of 1.04 W cm-2 at 750 °C and an electrolysis current density of 1.48 A cm-2 at 1.3 V, much greater than 0.64 W cm-2 and 1.02 A cm-2 of the cell with the pristine BGLC, respectively. This work provides a simple and effective surface chemistry modulation strategy for the development of an efficient air electrode for SOCs.

Controllable Technology for Thermal Expansion Coefficient of Commercial Materials for Solid Oxide Electrolytic Cells.

Solid oxide electrolysis cell (SOEC) industrialization has been developing for many years. Commercial materials such as 8 mol% Y2O3-stabilized zirconia (YSZ), Gd0.1Ce0.9O1.95 (GDC), La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF), La0.6Sr0.4CoO3-δ (LSC), etc., have been used for many years, but the problem of mismatched thermal expansion coefficients of various materials between cells has not been fundamentally solved, which affects the lifetime of SOECs and restricts their industry development. Currently, various solutions have been reported, such as element doping, manufacturing defects, and introducing negative thermal expansion coefficient materials. To promote the development of the SOEC industry, a direct treatment method for commercial materials-quenching and doping-is reported to achieve the controllable preparation of the thermal expansion coefficient of commercial materials. The quenching process only involves the micro-treatment of raw materials and does not have any negative impact on preparation processes such as powder slurry and sintering. It is a simple, low-cost, and universal research strategy to achieve the controllable preparation of the thermal expansion coefficient of the commercial material La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) through a quenching process by doping elements and increasing oxygen vacancies in the material. Commercial LSCF materials are heated to 800 °C in a muffle furnace, quickly removed, and cooled and quenched in 3.4 mol/L of prepared Y(NO3)3. The thermal expansion coefficient of the treated material can be reduced to 13.6 × 10-6 K-1, and the blank sample is 14.1 × 10-6 K-1. In the future, it may be possible to use the quenching process to select appropriate doping elements in order to achieve similar thermal expansion coefficients in SOECs.

Facile Construction of Nanostructured Cermet Anodes with Strong Metal-Oxide Interaction for Efficient and Durable Solid Oxide Fuel Cells.

Nanostructured anodes generate massive reaction sites to oxidize fuels in solid oxide fuel cells (SOFCs); however, the nonexistence of a practically viable approach for the construction of nanostructures and the retention of these nanostructures under the harsh operating conditions of SOFCs poses a significant challenge. Herein, a simple procedure is reported for the construction of a nanostructured Ni-Gd-doped CeO2 anode based on the direct assembly of pre-formed nanocomposite powder with strong metal-oxide interaction. The directly assembled anode forms heterointerfaces with the electrolyte owing to the electrochemical polarization current and exhibits excellent structural robustness against thermal ripening. An electrolyte-supported cell with the directly assembled anode produces a peak power density of 0.73 W cm-2 at 800 °C, while maintaining stability for 100 h, which is in contrast to the drastic degradation of the cermet anode prepared using the conventional method. These findings provide clarity on the design and construction of durable nanostructured anodes and other electrodes for SOFCs.

Investigation on Long-Term Stability of Vermiculite Seals for Reversible Solid Oxide Cell.

A reversible solid oxide cell (RSOC) integrating solid oxide fuel (SOFC) and a solid oxide electrolysis cell (SOEC) usually utilizes compressive seals. In this work, the vermiculite seals of various thickness and compressive load during thermal cycles and long-term operation were investigated. The leakage rates of seals were gradually increased with increasing thickness and input gas pressure. The thinner seals had good sealing performance. The compressive load was carried out at thinner seals, the possible holes were squeezed, and finally the leakage rates were lower. With a fixed input gas pressure of 1 psi, 2 psi, and 3 psi, the leakage rates of 0.50 mm vermiculite remained at around 0.009 sccm/cm, 0.017 sccm/cm and 0.028 sccm/cm during twenty thermal cycles, while the leakage rates remained at around 0.011 sccm/cm for about 240 h. Simultaneously, elemental diffusions between seals and components were limited, implying good compatibility. Furthermore, the open circuit voltage (OCV) remained at around 1.04 V during 17 thermal cycles, which is close to Nernst potentials. The stack performance confirmed that the vermiculite seals can meet the structural support and sealing requirements. Therefore, the vermiculite shows good promise for application in stacks during thermal cycles and long-term operation.

Ultrafine, Dual-Phase, Cation-Deficient PrBa0.8Ca0.2Co2O5+δ Air Electrode for Efficient Solid Oxide Cells.

Nanostructured air electrodes play a crucial role in improving the electrocatalytic activity of oxygen reduction and evolution reactions in solid oxide cells (SOCs). Herein, we report the fabrication of a nanostructured BaCoO3-decorated cation-deficient PrBa0.8Ca0.2Co2O5+δ (PBCC) air electrode via a combined modification and direct assembly approach. The modification approach endows the dual-phase air electrode with a large surface area and abundant oxygen vacancies. An intimate air electrode-electrolyte interface is in situ constructed with the formation of a catalytically active Co3O4 bridging layer via electrochemical polarization. The corresponding single cell exhibits a peak power density of 2.08 W cm-2, an electrolysis current density of 1.36 A cm-2 at 1.3 V, and a good operating stability at 750 °C for 100 h. This study provides insights into the rational design and facile utilization of an active and stable nanostructured air electrode of SOCs.

Molten Salt Synthesis of High-Performance, Nanostructured La0.6Sr0.4FeO3-δ Oxygen Electrode of a Reversible Solid Oxide Cell.

Nanoscale perovskite oxides with enhanced electrocatalytic activities have been widely used as oxygen electrodes of reversible solid oxide cells (RSOC). Here, La0.6Sr0.4FeO3-δ (LSF) nanoscale powder is synthesized via a novel molten salt method using chlorides as the reaction medium and fired at 850 °C for 5 h after removing the additives. A direct assembly method is employed to fabricate the LSF electrode without a pre-sintering process at high temperature. The microstructure characterization ensures that the direct assembly process will not damage the porosity of LSF. When operating as a solid oxide fuel cell (SOFC), the LSF cell exhibits a peak power density of 1.36, 1.07 and 0.7 W/cm2 at 800, 750 and 700 °C, respectively, while in solid oxide electrolysis cell (SOEC) mode, the electrolysis current density reaches 1.52, 0.98 and 0.53 A/cm2 under an electrolysis voltage of 1.3 V, respectively. Thus, it indicates that the molten salt routine is a promising method for the synthesis of highly active perovskite LSF powders for directly assembled oxygen electrodes of RSOC.

Fabrication of Lanthanum Strontium Manganite Ceramics via Agar Gel Casting and Solid State Sintering.

Fabricating lanthanum strontium manganite (LSM) ceramics with certain shapes is important for the design and construction of high-temperature energy conversion and storage devices. Here, we describe a low-cost and environmentally friendly method for fabricating LSM ceramics via agar gel casting and high temperature sintering. This new approach uses temperature tuning to fabricate LSM gel bodies, not only by manufacturing in the secondary process but also by remolding and recycling during the gel casting process. The effect of the sintering temperature on the properties of LSM ceramics was investigated as well. As a result, the porosity and compressive strength of LSM ceramics sintered at 1000 °C are ~60% and 5.6 MPa, respectively. When the sintering temperature increases to 1200 °C, the porosity decreases to ~28%, whereas the compressive strength increases to 25 MPa, which is able to meet the requirement of cathode-supported SOFCs (solid oxide fuel cells).

A Rechargeable High-Temperature Molten Salt Iron-Oxygen Battery.

The energy and power density of conventional batteries are far lower than their theoretical expectations, primarily because of slow reaction kinetics that are often observed under ambient conditions. Here we describe a low-cost and high-temperature rechargeable iron-oxygen battery containing a bi-phase electrolyte of molten carbonate and solid oxide. This new design merges the merits of a solid-oxide fuel cell and molten metal-air battery, offering significantly improved battery reaction kinetics and power capability without compromising the energy capacity. The as-fabricated battery prototype can be charged at high current density, and exhibits excellent stability and security in the highly charged state. It typically exhibits specific energy, specific power, energy density, and power density of 129.1 Wh kg-1 , 2.8 kW kg-1 , 388.1 Wh L-1 , and 21.0 kW L-1 , respectively, based on the mass and volume of the molten salt.

Syngas production by high temperature steam/CO2 coelectrolysis using solid oxide electrolysis cells.

High temperature (HT) steam/CO2 coelectrolysis with solid oxide electrolysis cells (SOECs) using the electricity and heat generated from clean energies is an important alternative for syngas production without fossil fuel consumption and greenhouse gas emissions. Herein, reaction characteristics and the outlet syngas composition of HT steam/CO2 coelectrolysis under different operating conditions, including distinct inlet gas compositions and electrolysis current densities, are systematically studied at 800 °C using commercially available SOECs. The HT coelectrolysis process, which has comparable performance to HT steam electrolysis, is more active than the HT CO2 electrolysis process, indicating the important contribution of the reverse water-gas shift reaction in the formation of CO. The outlet syngas composition from HT steam/CO2 coelectrolysis is very sensitive to the operating conditions, indicating the feasibility of controlling the syngas composition by varying these conditions. Maximum steam and CO2 utilizations of 77% and 76% are achieved at 1.0 A cm(-2) with an inlet gas composition of 20% H2/40% steam/40% CO2.