A fast ceramic mixed OH-/H+ ionic conductor for low temperature fuel cells.

Low temperature ionic conducting materials such as OH- and H+ ionic conductors are important electrolytes for electrochemical devices. Here we show the discovery of mixed OH-/H+ conduction in ceramic materials. SrZr0.8Y0.2O3-δ exhibits a high ionic conductivity of approximately 0.01 S cm-1 at 90 °C in both water and wet air, which has been demonstrated by direct ammonia fuel cells. Neutron diffraction confirms the presence of OD bonds in the lattice of deuterated SrZr0.8Y0.2O3-δ. The OH- ionic conduction of CaZr0.8Y0.2O3-δ in water was demonstrated by electrolysis of both H218O and D2O. The ionic conductivity of CaZr0.8Y0.2O3-δ in 6 M KOH solution is around 0.1 S cm-1 at 90 °C, 100 times higher than that in pure water, indicating increased OH- ionic conductivity with a higher concentration of feed OH- ions. Density functional theory calculations suggest the diffusion of OH- ions relies on oxygen vacancies and temporarily formed hydrogen bonds. This opens a window to discovering new ceramic ionic conducting materials for near ambient temperature fuel cells, electrolysers and other electrochemical devices.

Optimization of a Perovskite Oxide-Based Cathode Catalyst Layer on Performance of Direct Ammonia Fuel Cells.

To maximize fuel cell performance, transport pathways for electrons, ions, and reactants should be connected well. This demands a well-constructed microstructure in the catalyst layer (CL). Herein we design and optimize a cathode CL for a direct ammonia fuel cell (DAFC) using a perovskite oxide as the catalyst to reduce reliance on platinum group metals (PGMs). The effects of tailoring carbon, ionomer, and polytetrafluoroethylene (PTFE) content in cathode CLs (CCLs) were explored, and several DAFCs were tested. Using the same catalyst and operating conditions, the lowest maximum current density and peak power density obtained were 85.3 mA cm-2 and 5.92 mW cm-2, respectively, which substantially increased to 317 mA cm-2 and 30.1 mW cm-2 through proper carbon, ionomer, and PTFE optimization, illustrating the importance of an effective three-phase interface. The findings reveal that despite employment of an active catalyst for oxygen reduction at the cathode site, the true performance of the catalyst cannot be reflected unless it is supported by proper design of the CCL. The study also reveals that by optimizing the CCL, similar performances to those of Pt/C-based CCLs in literature can be obtained at a cost reduction.

An Efficient Symmetric Electrolyzer Based On Bifunctional Perovskite Catalyst for Ammonia Electrolysis.

Ammonia is a natural pollutant in wastewater and removal technique such as ammonia electro-oxidation is of paramount importance. The development of highly efficient and low-costing electrocatalysts for the ammonia oxidation reaction (AOR) and hydrogen evolution reaction (HER) associated with ammonia removal is subsequently crucial. In this study, for the first time, the authors demonstrate that a perovskite oxide LaNi0.5 Cu0.5 O3-δ after being annealed in Ar (LNCO55-Ar), is an excellent non-noble bifunctional catalyst towards both AOR and HER, making it suitable as a symmetric ammonia electrolyser (SAE) in alkaline medium. In contrast, the LNCO55 sample fired in air (LNCO55-Air) is inactive towards AOR and shows very poor HER activity. Through combined experimental results and theoretical calculations, it is found that the superior AOR and HER activities are attributed to the increased active sites, the introduction of oxygen vacancies, the synergistic effect of B-site cations and the different active sites in LNCO55-Ar. At 1.23 V, the assembled SAE demonstrates ≈100% removal efficiency in 2210 ppm ammonia solution and >70% in real landfill leachate. This work opens the door for developments towards bifunctional catalysts, and also takes a profound step towards the development of low-costing and simple device configuration for ammonia electrolysers.

N,N-Dimethylacetamide-Diluted Nitrate Electrolyte for Aqueous Zn//LiMn2O4 Hybrid Ion Batteries.

N,N-Dimethylacetamide (DMA) cooperated with LiNO3 salt has previously shown to be a promising electrolyte for a Li//O2 battery, showing good stability against both the O2 electrode reaction and Li stripping/plating. In this work, DMA is hybridized with a concentrated nitrate electrolyte [2.5 m Zn(NO3)2 + 13 m LiNO3 aqueous solution] for better electrochemical stability while using less dissolved salts. The widest electrochemical stability window for this DMA-diluted electrolyte is determined as 3.1 V, the negative critical stability potential of which is -1.6 V versus Ag/AgCl, indicating desirable stability against hydrogen evolution and Zn deposition. The findings can be attributed to the weakened Li+/Zn2+ solvation sheath caused by low permittivity of DMA, as revealed through Raman spectra characterization and molecular dynamics simulation. A Zn//Zn symmetrical cell and Zn//LiMn2O4 hybrid ion batteries are assembled in air directly, attributed to the stability of DMA toward O2. Zn stripping/plating with a dendrite-free morphology is delivered for 110 h and 200 charge/discharge cycles under 1 C rate, achieving 99.0% Coulombic efficiency. The maximum capacity of the battery is 121.0 mA h·g-1 under 0.2 C rate (based on the mass of LiMn2O4), delivering an energy density of 165.8 W h·kg-1 together with 2.0 V working voltage. This work demonstrates the feasibility and validity of utilizing a relatively dilute electrolyte dissolved in oxygen for a highly stable aqueous rechargeable battery.

Investigation of Perovskite Oxide SrCo0.8 Cu0.1 Nb0.1 O3-δ as a Cathode Material for Room Temperature Direct Ammonia Fuel Cells.

Single-phase perovskite oxide SrCo0.8 Cu0.1 Nb0.1 O3-δ was synthesized using a Pechini method. X-ray diffraction (XRD) analysis indicated a cubic structure with a=3.8806(7) Å. The oxide material was combined with active carbon, forming a composite electrode to be used as the cathode in a room temperature ammonia fuel cell based on an anion membrane electrolyte and NiCu/C anode. An open circuit voltage (OCV) of 0.19 V was observed with dilute 0.02 m (340 ppm) ammonia solution as the fuel. The power density and OCV were improved upon the addition of 1 m NaOH to the fuel, suggesting that the addition of NaOH, which could be achieved through the introduction of alkaline waste to the fuel stream, could improve performance when wastewater is used as the fuel. It was found that the SrCo0.8 Cu0.1 Nb0.1 O3-δ cathode was converted from irregular shape into shuttle-shape during the fuel cell measurements. As the key catalysts for electrode materials for this fuel cell are all inexpensive, after further development, this could be a promising technology for removal of ammonia from wastewater.

Growth of Compact CH3NH3PbI3 Thin Films Governed by the Crystallization in PbI2 Matrix for Efficient Planar Perovskite Solar Cells.

As a convenient preparation technique, a two-step method, which is normally done by spin-coating CH3NH3I onto PbI2 film followed by a thermal annealing, is generally used to prepare solution-processed CH3NH3PbI3 films for planar perovskite solar cells. Here, we prepare the compact CH3NH3PbI3 thin films by the two-step method at a low temperature (<80 °C) and investigate the effects of PbI2 crystallization on the structure-property correlation in the CH3NH3PbI3 films. It is found that the importance of the crystallization in PbI2 matrix lies in governing the transition from the (001) plane of trigonal PbI2 to the (002) plane of tetragonal CH3NH3PbI3 in the rapid reaction process for atoms to coordinate into perovskite during spin-coating, which actually determines the morphology and the type of vacancy defects in resulting perovskite; a better crystallized PbI2 film has a much stronger ability to react with CH3NH3I solution and produces larger CH3NH3PbI3 grains with a higher crystallinity. The CH3NH3PbI3/TiO2 planar solar cell derived from a better crystallized PbI2 film exhibits significantly improved performance and stability as the result of the higher crystallinity inside the perovskite film. Moreover, it is demonstrated that the crystalline PbI2 film matrix subjected to the annealing after a slow heating process prior to contacting CH3NH3I solution is more effective for CH3NH3PbI3 formation than that with a direct annealing history. The results in this paper provide a guide for preparing high-quality CH3NH3PbI3 thin films for efficient perovskite solar cells and CH3NH3PbI3 interfacial films over the layers susceptible to temperature.

A perovskite oxide with high conductivities in both air and reducing atmosphere for use as electrode for solid oxide fuel cells.

Electrode materials which exhibit high conductivities in both oxidising and reducing atmospheres are in high demand for solid oxide fuel cells (SOFCs) and solid oxide electrolytic cells (SOECs). In this paper, we investigated Cu-doped SrFe0.9Nb0.1O3-δ finding that the primitive perovskite oxide SrFe0.8Cu0.1Nb0.1O3-δ (SFCN) exhibits a conductivity of 63 Scm(-1)and 60 Scm(-1) at 415 °C in air and 5%H2/Ar respectively. It is believed that the high conductivity in 5%H2/Ar is related to the exsolved Fe (or FeCu alloy) on exposure to a reducing atmosphere. To the best of our knowledge, the conductivity of SrFe0.8Cu0.1Nb0.1O3-δ in a reducing atmosphere is the highest of all reported oxides which also exhibit a high conductivity in air. Fuel cell performance using SrFe0.8Cu0.1Nb0.1O3-δ as the anode, (Y2O3)0.08(ZrO2)0.92 as the electrolyte and La0.8Sr0.2FeO3-δ as the cathode achieved a power density of 423 mWcm(-2) at 700 °C indicating that SFCN is a promising anode for SOFCs.

A simple high-performance matrix-free biomass molten carbonate fuel cell without CO2 recirculation.

In previous reports, flowing CO2 at the cathode is essential for either conventional molten carbonate fuel cells (MCFCs) based on molten carbonate/LiAlO2 electrolytes or matrix-free MCFCs. For the first time, we demonstrate a high-performance matrix-free MCFC without CO2 recirculation. At 800°C, power densities of 430 and 410 mW/cm(2) are achieved when biomass-bamboo charcoal and wood, respectively-is used as fuel. At 600°C, a stable performance is observed during the measured 90 hours after the initial degradation. In this MCFC, CO2 is produced at the anode when carbon-containing fuels are used. The produced CO2 then dissolves and diffuses to the cathode to react with oxygen in open air, forming the required [Formula: see text] or [Formula: see text] ions for continuous operation. The dissolved [Formula: see text] ions may also take part in the cell reactions. This provides a simple new fuel cell technology to directly convert carbon-containing fuels such as carbon and biomass into electricity with high efficiency.

Titanate cathodes with enhanced electrical properties achieved via growing surface Ni particles toward efficient carbon dioxide electrolysis.

Ionic conduction in perovskite oxide is commonly tailored by element doping in lattices to create charge carriers, while few studies have been focused on ionic conduction enhancement through tailoring microstructures. In this work, remarkable enhancement of ionic conduction in titanate has been achieved via in situ growing active nickel nanoparticles on an oxide surface by controlling the oxide material nonstoichiometry. The combined use of XRD, SEM, XPS and EDS indicates that the exsolution/dissolution of the nickel nanoparticles is completely reversible in redox cycles. With the synergetic effect of enhanced ionic conduction of titanate and the presence of catalytic active Ni nanocatalysts, significant improvement of electrocatalytic performances of the titanate cathode is demonstrated. A current density of 0.3 A cm(-2) with a Faradic efficiency of 90% has been achieved for direct carbon dioxide electrolysis in a 2 mm-thick YSZ-supported solid oxide electrolyzer with the modified titanate cathode at 2 V and 1073 K.

Synthesis of ammonia directly from wet air using Sm(0.6)Ba(0.4)Fe(0.8)Cu(0.2)O(3-δ) as the catalyst.

Ammonia was directly synthesised from wet air at 400 °C at atmospheric pressure. A new perovskite Sm(0.6)Ba(0.4)Fe(0.8)Cu(0.2)O(3-δ) was used as the electrocatalyst for electrochemical synthesis of ammonia. Ammonia formation rates of 9.19 × 10(-7) mol s(-1) m(-2) and 1.53 × 10(-6) mol s(-1) m(-2) were obtained at 400 °C when wet air and wet N2 were introduced into a simple single chamber reactor, respectively. The perovskite catalyst is low cost compared to the previously reported Ru/MgO and Pt/C catalysts. This experiment indicates that ammonia can be directly synthesised from wet air, a very promising simple technology for sustainable synthesis of ammonia in the future.

High ionic conductivity in a LiFeO2-LiAlO2 composite under H2/air fuel cell conditions.

New ionic conducting materials for electrolytes for electrochemical devices have been attracting the interest of researchers in energy materials. Here, for the first time, we report a conductive composite with high ionic conductivity derived from an electronic conductor α-LiFeO2 and an insulator γ-LiAlO2. High conductivity was observed in the α-LiFeO2-γ-LiAlO2 composite when prepared by a solid state reaction method. However, the conductivity enhancement in α-LiFeO2-γ-LiAlO2 composite was not observed when the two oxides were mechanically mixed. The α-LiFeO2-γ-LiAlO2 composite also exhibits O(2-) or/and H(+) ionic conduction which was confirmed through H2/air fuel cell measurements. An exceptionally high conductivity of 0.50 S cm(-1) at 650 °C was observed under H2/air fuel cell conditions. This provides a new approach to discover novel ionic conductors from composite materials derived from electronic conductors.

Preparation of silver nanoparticles by a non-aqueous sol-gel process.

Using a non-aqueous sol-gel process with a direct calcination step in air after prior drying, silver nanoparticles with average size distribution ranging from 20 to 100 nm were synthesised. Studies in reduced atmosphere were also performed with mixed results, both in phase and particle size, as the samples were found to be mixed with an amorphous phase. In oxidising atmosphere, the temperature and dwelling time were found to be critical factors with the former playing a larger role than the latter. Optimally nanoparticles of silver are best prepared by direct calcination in air of the precursor gel at 250 degrees C for 1 hour. Compared to silver particles prepared by microemulsions, the particle size is larger due to the thermal treatment, which causes a growth of the silver particles.

Synthesis of ammonia directly from air and water at ambient temperature and pressure.

The N≡N bond (225 kcal mol⁻¹) in dinitrogen is one of the strongest bonds in chemistry therefore artificial synthesis of ammonia under mild conditions is a significant challenge. Based on current knowledge, only bacteria and some plants can synthesise ammonia from air and water at ambient temperature and pressure. Here, for the first time, we report artificial ammonia synthesis bypassing N2 separation and H2 production stages. A maximum ammonia production rate of 1.14 × 10⁻5 mol m⁻² s⁻¹ has been achieved when a voltage of 1.6 V was applied. Potentially this can provide an alternative route for the mass production of the basic chemical ammonia under mild conditions. Considering climate change and the depletion of fossil fuels used for synthesis of ammonia by conventional methods, this is a renewable and sustainable chemical synthesis process for future.

Methane oxidation at redox stable fuel cell electrode La0.75Sr0.25Cr0.5Mn0.5O(3-delta).

Because of its widespread availability, natural gas is the most important fuel for early application of stationary fuel cells, and furthermore, methane containing biogases are one of the most promising renewable energy alternatives; thus, it is very important to be able to efficiently utilize methane in fuel cells. Typically, external steam reforming is applied to allow methane utilization in high temperature fuel cells; however, direct oxidation will provide a much better solution. Recently, we reported good electrochemical performance for an oxide anode La0.75Sr0.25Cr0.5Mn0.5O3 (LSCM) in low moisture (3% H2O) H2 and CH4 fuels without significant coking in CH4. Here, we investigate the catalytic activity of this oxide with respect to its ability to utilize methane. This oxide is found to exhibit fairly low reforming activity for both H2O and CO2 reforming but is active for methane oxidation. LSCM is found to be a full oxidation catalyst rather than a partial oxidation catalyst as CO2 production dominates CO production even in CH4-rich CH4/O2 mixtures. X-ray adsorption spectroscopy was utilized to confirm that Mn was the redox active species, clearly demonstrating that this material has the oxidation catalytic behavior that might be expected from a Mn perovskite and that the Cr ion is only present to ensure stability under fuel atmospheres.

Discovery and characterization of novel oxide anodes for solid oxide fuel cells.

The search for alternative anode materials for solid oxide fuel cells (SOFCs) has been reviewed in the light of structure, stability, conductivity, chemical and thermal compatibility with electrolyte YSZ. In this review, we have presented the advantages and disadvantages of the traditional Ni-YSZ anode for SOFCs. The development of alternative anode for SOFCs with fluorite, rutile, tungsten bronze, pyrochlore, perovskite and spinel structures has been reviewed and discussed in detail. Among the reported materials systems, materials with perovskite structure are promising particularly where two ions with complimentary function are present on the B-site at high concentration. We have recently found a good redox stable anode (La(0.75)Sr(0.25))(1-x)Cr(0.5)Mn(0.5)O(3) (0

A redox-stable efficient anode for solid-oxide fuel cells.

Solid-oxide fuel cells (SOFCs) promise high efficiencies in a range of fuels. Unlike lower temperature variants, carbon monoxide is a fuel rather than a poison, and so hydrocarbon fuels can be used directly, through internal reforming or even direct oxidation. This provides a key entry strategy for fuel-cell technology into the current energy economy. Present development is mainly based on the yttria-stabilized zirconia (YSZ) electrolyte. The most commonly used anode materials are Ni/YSZ cermets, which display excellent catalytic properties for fuel oxidation and good current collection, but do exhibit disadvantages, such as low tolerance to sulphur and carbon deposition when using hydrocarbon fuels, and poor redox cycling causing volume instability. Here, we report a nickel-free SOFC anode, La0.75Sr0.25Cr0.5Mn0.5O3, with comparable electrochemical performance to Ni/YSZ cermets. The electrode polarization resistance approaches 0.2 Omega cm2 at 900 degrees C in 97% H2/3% H2O. Very good performance is achieved for methane oxidation without using excess steam. The anode is stable in both fuel and air conditions, and shows stable electrode performance in methane. Thus both redox stability and operation in low steam hydrocarbons have been demonstrated, overcoming two of the major limitations of the current generation of nickel zirconia cermet SOFC anodes.