Nanostructured Fe-N-C as bifunctional catalysts for oxygen reduction and hydrogen evolution

The development of electrocatalysts for energy conversion and storage devices is of paramount importance to promote sustainable development. Among the different families of materials, catalysts based on transition metals supported on a nitrogen-containing carbon matrix have been found to be effective catalysts toward oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER) with high potential to replace conventional precious metal-based catalysts. In this work, we developed a facile synthesis strategy to obtain a Fe-N-C bifunctional ORR/HER catalysts, involving wet impregnation and pyrolysis steps. Iron (II) acetate and imidazole were used as iron and nitrogen sources, respectively, and functionalized carbon black pearls were used as conductive support. The bifunctional performance of the Fe-N-C catalyst toward ORR and HER was investigated by cyclic voltammetry, rotating ring disk electrode experiments, and electrochemical impedance spectroscopy in alkaline environment. ORR onset potential and half-wave potential were 0.95 V and 0.86 V, respectively, indicating a competitive performance in comparison with the commercial platinum-based catalyst. In addition, Fe-N-C had also a good HER activity, with an overpotential of 478 mV @10 mAcm(-2) and Tafel slope of 133 mVdec(-1), demonstrating its activity as bifunctional catalyst in energy conversion and storage devices, such as alkaline microbial fuel cell and microbial electrolysis cells

Electrochemical characterization of anode supported SOFC prepared by co-firing technique

One of the main problems in the fabrication of anode supported solid oxide fuel cells is related to the sintering of electrolyte layer on anodic substrate, because differential densification of the layers may result in cracks during thermal process. Co-firing approach consists of simultaneous sintering of both electrolyte and anode. In this way, shrinkage of porous layer is compatible with the densification of electrolyte film. In this work co-firing technique was used for the sintering of YSZ thick films deposited on green NiO-YSZ layers by electrophoretic deposition (EPD). EPD is a colloidal process based on the motion of charged particles in the electric field in the direction of the electrode with opposite charge, thus forming a compact layer. With respect to other techniques, EPD has several advantages: short formation times, little restriction in the shape of substrates, simple deposition apparatus, possibility to have a mass production, low cost, easy control of the thickness of the deposited film through simple regulation of applied potential and deposition time. The EPD/co-firing combined process allowed to obtain a dense, 10 μm thick, crack free electrolyte layer with a good bonding to the anode. A slurry was prepared starting from a commercial NiOYSZ anodic powder (Praxair), polyvinylidene fluoride (PVDF binder SOLEF 6020, Solvay), a nanometric carbon powder (super P, Carbon Belgium), dispersed in N-methyl-2-pyrrolidone. A green membrane was obtained after evaporation of the solvent. A suspension of YSZ powder was prepared starting from commercial YSZ (TZ8Y, Tosoh) in methanol and deposited by EPD on a green NiO-YSZ membrane using a planar EPD cell setup. Co-firing parameters were assessed from the results of TG-DTA analysis performed on green bodies. Figure 1 shows the results of Hg porosimetry performed on sintered anodes for the determination of residual porosity and surface area. Green and fired samples were characterized in terms of morphology by scanning electron microscopy (FE-SEM), as reported in Figure 2. EDS linescan performed on the cross section of the cell did not show nickel diffusion in the electrolyte layer. A cathode layer was deposited on fully sintered half cells via spray-powder technique, using a suspension of commercial LSFC powder (Nextech), followed by a low temperature sintering process. Electrochemical characterization was performed on button cells in hydrogen in the temperature range 600-800 degrees C. Data of the electrochemical characterization will be presented at the conference

Co-sintering of dense electrophoretically deposited YSZ films on porous NiO-YSZ substrates for SOFC applications

An original process for the preparation of YSZ dense films with a thickness lower than 10 μm over NiO-YSZ substrates is presented. This process involves the preparation of a green membrane of NiO-YSZ and subsequent electrophoretic deposition (EPD) of commercial YSZ powder on this polymer-rich membrane. A single thermal treatment allowed removal of the organic compounds, sintering of the layers and full densification of the electrolyte. © 2005 Materials Research Society

Lithium and proton conducting gel-type membranes

We review the characteristics and the properties of various types of gel-type, ionically conducting membranes. We have mainly investigated two classes of membranes, one characterized by lithium ion transport and the other characterized by proton conductivity. We show that the former membranes are suitable to be used as separators in advanced lithium ion plastic batteries and that the latter show good promises to be considered as alternative, new separators in polymer electrolyte fuel cells. © 2003 Elsevier B.V. All rights reserved

A covalent organic/inorganic hybrid proton exchange polymeric membrane: synthesis and characterization

Commercial polyetheretherketone (Victrex PEEK) was sulfonated up to 90% degree of sulfonation (DS), then reacted with SiCl4 to obtain a hybrid polymer. The product was characterized by 29-Si NMR and ATR/FTIR spectroscopies demonstrating the formation of covalent bonds between the organic and inorganic components. No dispersed inorganic silicon was present in the product as evidenced by the lack of any resonance at 100 ppm. Despite the high DS the physicochemical properties of the hybrid were suitable for the preparation of membranes exhibiting high and stable conductivity values (10K2 S/cm), hence suitable for application as ion exchange membrane

Redox-active coordination polymers as bifunctional electrolytes in slurry-based aqueous batteries at neutral pH

Highly water-dispersible, redox-active 1D coordination polymers (CPs) have been synthesized using low-cost precursors. These CPs, containing chloranilic acid as organic ligand and a transition element, such as Fe and Mn as a metal center, form long-term stable slurries containing up to 100 g/L solid particles in aqueous media (0.5 M NaCl, 1 mg carbon nanotubes). Voltammetry studies showed that the iron-based particulate slurries exhibited three different redox stages with no metal plating. However, the suspensions with manganese-based coordination polymers experienced a metal plating process in the same potential window range as for the iron-based CPs. Moreover, the particulate suspension of iron-CPs shown longer-term stability than their isostructural analogs based on manganese. The 1D Fe-CPs were used as catholyte and anolyte in a symmetrical cell with a low-cost size exclusion cellulose membrane acting as a separator. The cell experienced a reversible capacity value of 45 mAh/g (225 mAh/L) at a current density value of 20 mA/g for 50 cycles (~12 days) at neutral pH. This study opens the possibility of using inexpensive coordination polymers as single bifunctional electrolyte material in aqueous batteries and other sustainable energy storage-related systems

Sulfonated polyether ether ketone-based composite membranes doped with a tungsten-based inorganic proton conductor for fuel cell applications

Sulfonated polyether ether ketone (SPEEK)-based composite membranes doped with hydrated tungsten oxide were prepared and studied for proton exchange membrane applications. Hydrated tungsten oxide (W O3 ·2 H2 O) was synthesized via acidic hydrolysis of sodium tungstate and its structure and physicochemical features were investigated by thermogravimetric analysis (TG), X-ray diffraction (XRD), and electrochemical impedance spectroscopy (EIS). SPEEK/ W O3 ·2 H2 O composite membranes were prepared by mixing proper amounts of SPEEK and hydrated W O3 in dimethylacetamide as casting solvent. The composite membranes were characterized by XRD, TG-DTA, EIS, and water uptake measurements as a function of the oxide content in the membrane. In particular, XRD patterns as well as TG measurements indicated the existence of a coordinative interaction between the water molecules of tungsten oxide and the SPEEK sulfonic acid groups. This interaction lead to the enhancement of the membrane proton conductivity, as well as of their properties, from the point of view of heat resistance and water solubility. In fact, the addition of tungsten oxide resulted in higher proton conductivity, improved heat resistance, and lower water solubility. © 2006 The Electrochemical Society. All rights reserved

Investigating the factors that influence resistance rise of PIM-1 membranes in nonaqueous electrolytes

As redox active macromolecules are introduced to the materials repertoire of redox flow batteries (RFBs), nanoporous membranes, such as polymers of intrinsic microporosity (PIMs), are emerging as a viable separation strategy. Although their selectivity has been demonstrated, PIM-based membranes suffer from time-dependent resistance rise in nonaqueous electrolytes. Here, we study this phenomenon as a function of membrane thickness, electrolyte flow rate, and solvent washing using a diagnostic flow cell configuration. We find that the rate and magnitude of resistance rise can be significantly reduced through the combination of low electrolyte flow rate and solvent prewash. Further, our results indicate that, since the increase is not associated with irreversible chemical and structural changes, the membrane performance can be recovered via ex-situ or in-situ solvent washes. Keywords: Energy storage, Redox flow battery, Polymer of intrinsic microporosity, Size-exclusion membranes, Performance recovery, Cell resistanc