Conformal Electrocatalytic Surface Nanoionics for Accelerating High-Temperature Electrochemical Reactions in Solid Oxide Fuel Cells.

Additive implantation of electrocatalysts onto the internal surface of porous cathodes holds great promise to accelerate the electrochemical reactions within solid oxide fuel cells (SOFCs). Here we utilize atomic layer deposition (ALD) to apply dual catalysts with (Mn0.8Co0.2)3O4 and a minute amount of Pt on the cathode consisting of lanthanum strontium manganite (LSM) and yttria-stabilized zirconia (YSZ). Coating this material with optimum ALD layer thickness resulted in a 53% reduction of polarization resistance and a 350% SOFC peak power density enhancement at 750 °C. During the electrochemical operations, the dual catalysts interact synergistically and evolve into superjacent conformal electrocatalytic (Mn0.8Co0.2)3O4 nanoionics with high-density grain boundaries and subjacent discrete nano Pt particles evenly distributed on both the LSM and YSZ. The configuration consequently extends the active electrochemical reaction sites to the entire internal surface of the cathode. For the first time in the field of SOFCs, the present work demonstrates the formation of the electrocatalytic surface nanoionics and its resultant accelerated mass and charge transfer to dramatically boost the cell performance.

Quantitative interpretation of impedance spectroscopy data on porous LSM electrodes using X-ray computed tomography and Bayesian model-based analysis.

It is broadly understood that strontium-doped lanthanum manganate (LSM) cathodes for solid oxide fuel cells (SOFCs) have two pathways for the reduction of oxygen: a surface-mediated pathway culminating in oxygen incorporation into the electrolyte at the triple-phase boundary (TPB), and a bulk-mediated pathway involving oxygen transfer across the electrode-electrolyte interface. Patterned electrode and thin film experiments have shown that both pathways are active in LSM. Porous electrode geometries more commonly found in SOFCs have not been amenable for precise measurement of active electrode width because of the difficulty in precisely measuring the electrode geometry. This study quantitatively compares a reaction-diffusion model for the oxygen reduction reaction in LSM to the impedance spectrum of an experimental LSM porous electrode symmetric button cell on a yttria-stabilized zirconia (YSZ) electrolyte. The porous microstructure was characterized using computed tomography (nano-CT) and Bayesian model-based analysis (BMA) was used to estimate model parameters. BMA produced good fits to the data, with higher than expected values for the interfacial capacitance at the LSM-YSZ interface and vacancy diffusion activation energy; these results may indicate that the active width of the electrode is on a similar scale with that of the space-charge width at the LSM-YSZ interface. The analysis also showed that the active width and proportion of current moving through the bulk pathway is temperature dependent, in accordance with patterned electrode results.

Nanoionics and Nanocatalysts: Conformal Mesoporous Surface Scaffold for Cathode of Solid Oxide Fuel Cells.

Nanoionics has become increasingly important in devices and systems related to energy conversion and storage. Nevertheless, nanoionics and nanostructured electrodes development has been challenging for solid oxide fuel cells (SOFCs) owing to many reasons including poor stability of the nanocrystals during fabrication of SOFCs at elevated temperatures. In this study, a conformal mesoporous ZrO2 nanoionic network was formed on the surface of La1-xSrxMnO3/yttria-stabilized zirconia (LSM/YSZ) cathode backbone using Atomic Layer Deposition (ALD) and thermal treatment. The surface layer nanoionic network possesses open mesopores for gas penetration, and features a high density of grain boundaries for enhanced ion-transport. The mesoporous nanoionic network is remarkably stable and retains the same morphology after electrochemical operation at high temperatures of 650-800 °C for 400 hours. The stable mesoporous ZrO2 nanoionic network is further utilized to anchor catalytic Pt nanocrystals and create a nanocomposite that is stable at elevated temperatures. The power density of the ALD modified and inherently functional commercial cells exhibited enhancement by a factor of 1.5-1.7 operated at 0.8 V at 750 °C.