Alternative Strategy for Development of Dielectric Calcium Copper Titanate-Based Electrolytes for Low-Temperature Solid Oxide Fuel Cells.

The development of low-temperature solid oxide fuel cells (LT-SOFCs) is of significant importance for realizing the widespread application of SOFCs. This has stimulated a substantial materials research effort in developing high oxide-ion conductivity in the electrolyte layer of SOFCs. In this context, for the first time, a dielectric material, CaCu3Ti4O12 (CCTO) is designed for LT-SOFCs electrolyte application in this study. Both individual CCTO and its heterostructure materials with a p-type Ni0.8Co0.15Al0.05LiO2-δ (NCAL) semiconductor are evaluated as alternative electrolytes in LT-SOFC at 450-550 °C. The single cell with the individual CCTO electrolyte exhibits a power output of approximately 263 mW cm-2 and an open-circuit voltage (OCV) of 0.95 V at 550 °C, while the cell with the CCTO-NCAL heterostructure electrolyte capably delivers an improved power output of approximately 605 mW cm-2 along with a higher OCV over 1.0 V, which indicates the introduction of high hole-conducting NCAL into the CCTO could enhance the cell performance rather than inducing any potential short-circuiting risk. It is found that these promising outcomes are due to the interplay of the dielectric material, its structure, and overall properties that led to improve electrochemical mechanism in CCTO-NCAL. Furthermore, density functional theory calculations provide the detailed information about the electronic and structural properties of the CCTO and NCAL and their heterostructure CCTO-NCAL. Our study thus provides a new approach for developing new advanced electrolytes for LT-SOFCs.

Doubly Occupied Pair Coupled Cluster F12 Approach.

Inspired by reports of the good performance of the doubly occupied pair coupled cluster (pCCD) theory in describing static electron correlation, we have introduced and implemented a variant thereof that includes single excitations and explicitly treats the dynamic electron correlation using the F12 methodology (pCCSD-F12). This drastically reduces the computation scaling with respect to the standard method using the full double-excitation operator (CCSD-F12). Slater-type geminals as a correlation factor, together with fixed cusp conditions, were used, which is known as the SP-ansatz. For sample model systems, we have investigated the performance of reference states constructed from either canonical or localized molecular orbitals. Finaly, the employment of Brueckner orbitals has been tested, which causes the single excitations to naturally vanish from the wave function expansion (B-pCCD-F12). Our test systems include different-sized rings of hydrogen atoms and dissociation curves for small molecules such as HF, N2, and CO2; and comparison with CCSD-F12 is presented for a series of reaction enthalpies.