High performance cobalt-free perovskite cathode for intermediate temperature solid oxide fuel cells

Bi doping of SrFeO3d results in the formation of a structure with high symmetry and extraordinary electrochemical performance for Bi0.5Sr0.5FeO3-d, which is capable of competing effectively with the current Co-based cathode benchmark with additional advantages of lower thermal expansion and cost.

Characterization and evaluation of BaCo0.7Fe0.2Nb0.1O3−δ as a cathode for proton-conducting solid oxide fuel cells

This study characterizes BaCo0.7Fe0.2Nb0.1O3−δ (BCFN) perovskite oxide and evaluates it as a potential cathode material for proton-conducting SOFCs with a BaZr0.1Ce0.7Y0.2O3-δ (BZCY) electrolyte. A four-probe DC conductivity measurement demonstrated that BCFN has a modest electrical conductivity of 2–15 S cm−1 in air with p-type semiconducting behavior. An electrical conductivity relaxation test showed that BCFN has higher Dchem and Kchem than the well-known Ba0.5Sr0.5Co0.8Fe0.2O3−δ oxide. In addition, it has relatively low thermal expansion coefficients (TECs) with values of 18.2 × 10−6 K−1 and 14.4 × 10−6 K−1 at temperature ranges of 30–900 °C and 30–500 °C, respectively. The phase reaction between BCFN and BZCY was investigated using powder and pellet reactions. EDX and XRD characterizations demonstrated that BCFN had lower reactivity with the BZCY electrolyte than strontium-containing perovskite oxides such as SrCo0.9Nb0.1O3-δ and Ba0.6Sr0.4Co0.9Nb0.1O3−δ. The impedance of BCFN was oxygen partial pressure dependent. Introducing water into the cathode atmosphere reduced the size of both the high-frequency and low-frequency arcs of the impedance spectra due to facilitated proton hopping. The cathode polarization resistance and overpotential at a current density of 100 mA cm−2 were 0.85 Ω cm−2 and 110 mV in dry air, which decreased to 0.43 Ω cm−2 and 52 mV, respectively, in wet air (∼3% H2O) at 650 °C. A decrease in impedance was also observed with polarization time; this was possibly caused by polarization-induced microstructure optimization. A promising peak power density of ∼585 mW cm−2 was demonstrated by an anode-supported cell with a BCFN cathode at 700 °C.

Deactivation and regeneration of oxygen reduction reactivity on double perovskite Ba2Bi0.1Sc0.2Co1.7O6−x cathode for intermediate-temperature solid oxide fuel cells

in situ high-temperature X-ray diffraction and thermal gravimetric- differential thermal analysis on room-temperature powder, as well as X-ray diffraction, Raman spectroscopy, and transmission electron microscopy on quenched powder, were applied to study crystal structure and phase transformations in Ba₂Bi_0.1Sc_0.2Co _1.7O_6-x (BBSC). Heating BBSC in air to over 800 °C produces a pure cubic phase with space group Fm3m (no. 225), and cooling down below 800 °C leads to a mixture of three noncubic phases including an unknown phase between 200 and 650 °C, a 2H hexagonal BaCoO3 with space group P63/mmc (no. 194) between 600 and 800 °C, and an intermediate phase at 800 °C. These three phases exist concurrently with the major cubic phase. The weight gain and loss between 300 and 900 °C suggest the occurrence of cobalt reduction, oxidation, and disproportion reactions with dominant reduction reaction at above 600 °C. The thermal expansion of BBSC was also examined by dilatometry. BBSC has a highly temperature-dependent thermal expansion coefficient which relates well with its structure evolution. Furthermore, the oxygen reduction reaction (ORR) of BBSC was probed by symmetrical cell and three-electrode configurations. The presence of hexagonal phase at 700 °C rarely affects the ORR performance of BBSC as evidenced by a slight increase of its area-specific resistance (ASR) value following 48 h of testing in this three-electrode configuration. This observation is in contrast to the commonly held point of view that noncubic phase deteriorates performance of perovskite compounds (especially in oxygen transport applications). Moreover, cathodic polarization treatment, for example, current discharge from BBSC (tested in three-electrode configuration), can be utilized to recover the original ORR performance. The cubic structure seems to be retained on the cathodic polarization - the normal cathode operating mode in fuel cells. Stable 72-h performance of BBSC in cathodic polarization mode further confirms that despite the presence of phase impurities, BBSC still demonstrates good performance between 500 and 700 °C, the desired intermediate operating temperature in solid oxide fuel cells.

A single-step synthesized cobalt-free barium ferrites-based composite cathode for intermediate temperature solid oxide fuel cells

Cobalt-free perovskite cathode with excellent oxygen reduction reaction (ORR) properties below 800 °C is a key material toward wide implementation of intermediate-temperature solid oxide fuel cells. This work reports the phase structure, microstructure and performance of such cathode based on the composite phases of triclinic Ba0.9Bi0.1FeO3-δ, cubic BaFeO3 and orthorhombic BaFe2O4 prepared by sol–gel route. The resultant barium ferrites composite cathode exhibits uniform particles, pores and elements distribution. In particular, favorable ORR properties of this cathode is demonstrated by very low interfacial resistance of only 0.036 and 0.072 Ω cm2 at 750 and 700 °C and maximum power density of 1295 and 840 mW cm−2 at 750 and 700 °C.

Fuel cells for the classroom

High mobility I− / I3− redox couple in a molecular plastic crystal: A potential new generation of electrolyte for solid-state photoelectrochemical cells

A series of new electrolyte materials based on a molecular plastic crystal doped by different iodide salts together with iodine have been prepared and characterized by thermal analysis, ionic conductivity, electrochemical and solid-state NMR diffusion measurements. In these materials, the plastic crystal phase of succinonitrile acts as a good matrix for the quaternary ammonium based iodides and iodine and appears to act in some cases as a solid-state “solvent” for the binary dopants. The materials were prepared by mixing the components in the molten state with subsequent cooling into the plastic crystalline state. This resulted in waxy-solid electrolytes in the temperature range from − 40 to 60 °C. The combination of structural variation of the cations, and fast redox couple diffusion (comparable with liquid-based electrolytes), as well as a high ionic conductivity of up to 3 × 10^{− 3} S cm^{− 1} at ambient temperature, make these materials very attractive for potential use in solid-state photoelectrochemical cells.

Rapid I−/I3− diffusion in a molecular-plastic-crystal electrolyte for potential application in solid-state photoelectrochemical cells

High current-carrying capacity and rapid, liquidlike diffusion were achieved in a dye-sensitized solar cell (DSSC) based on the plastic-crystalline electrolyte succinonitrile and the I⁻/I₃⁻ redox couple (see diagram). This could lead to the development of true solid-state DSSCs without conventional organic-liquid electrolytes, which can cause problems with long-term device stability.

Platinum electrodeposition for polymer electrolyte membrane fuel cells

A novel electrodeposition technique for preparing the catalyst layer in polymer electrolyte membrane fuel cells has been designed, which may enable an increase in the level of platinum utilisation currently achieved in these systems. This method consists of a two-step procedure involving the impregnation of platinum ions into a preformed catalyst layer (via an ion-exchange into the Nafion polymer electrolyte), followed by a potentiostatic reduction. The concentration of Nafion within the catalyst layer was found to have a significant bearing on the size of the platinum deposits. The preparation of catalyst layers containing a desired platinum loading should also be possible using this method. Surface areas of the platinum deposits were determined using cyclic voltammetry. The prepared catalyst was compared with a conventional electrode made from E-TEK Pt/C. Scanning electron microscopy was used to investigate the dispersion of the platinum particles. Platinum loadings were determined quantitatively by atomic absorption spectroscopy.

A three-dimensional highly interconnected composite oxygen reduction reaction electrocatalyst prepared from a core-shell precursor

Getting intimate: A 3D interconnected Bi_0.5Sr _0.5FeO_3-ð (BSF)-Ag electrocatalyst is prepared from a BSF-AgNO₃ core-shell precursor in one step. The nanometer-sized Ag enhances the sintering process, enabling an optimum cathode microstructure and good cathode-to-electrolyte attachment upon firing at 850°C. A solid-oxide fuel cell based on this cathode shows a near 100% peak power density enhancement at 550°C.

Integrated High-Efficiency Pt/Carbon Nanotube Arrays for PEM Fuel Cells

A facile strategy to deposit Pt nanoparticles with various metal-loading densities on vertically aligned carbon nanotube (ACNT) arrays as electrocatalysts for proton exchange membrane (PEM) fuel cells is described. The deposition is achieved by electrostatic adsorption of the Pt precursor on the positively charged polyelectrolyte functionalized ACNT arrays and subsequent reduction by L-ascorbic acid. The application of the aligned electrocatalysts in fuel cells is realized by transferring from a quartz substrate to nafion membrane using a hot-press procedure to fabricate the membrane electrode assembly (MEA). It is shown that the MEA with vertically aligned structured electrocatalysts provides better Pt utilization than that with Pt on conventional carbon nanotubes or carbon black, resulting in higher fuel cell performance.

Carbon nanotube architectures as catalyst supports for proton exchange membrane fuel cells

Catalyst support materials exhibit great influence on the performance and durability of proton exchange membrane (PEM) fuel cells. This minireview article summarises recent developments into carbon nanotube-based support materials for PEM fuel cells, including the membrane electrode assembly (MEA). The advantages of using CNTs to promote catalyst performance and stability, a perspective on research directions and strategies to improve fuel cell performance and durability are discussed. It is hoped that this minireview will act as a conduit for future developments in catalyst supports and MEA design for PEM fuel cells.