A novel MEA architecture for improving the performance of a DMFC

Direct methanol fuel cell (DMFC) consisting of a double-catalytic layered membrane electrode assembly (MEA) provide higher performance than that with the traditional MEA. This novel structured MEA includes a hydrophilic inner catalyst layer and a traditional electrode with an outer catalyst layer, which was made using both catalyst coated membrane (CCM) and gas diffusion electrode (GDE) methods. The inner catalyst was PtRu black on anode and Pt black on cathode. The outer catalyst was carbon supported Pt–Ru/Pt on anode and cathode, respectively. Thus in the double-catalytic layered electrodes three gradients were formed: catalyst concentration gradient, hydrophilicity gradient and porosity gradient, resulting in good mass transfer, proton and electron conducting and low methanol crossover. The peak density of DMFC with such MEA was 19 mW cm⁻², operated at 2 M CH₃OH, 2 atm oxygen at room temperature, which was much higher than DMFC with traditional MEA.     

A novel single electrode supported direct methanol fuel cell

In this paper a single electrode supported direct methanol fuel cell (DMFC) is fabricated and tested. The novel architecture combines the elimination of the polymer electrolyte membrane (PEM) and the integration of the anode and cathode into one component. The thin film fabrication involves a sequential deposition of an anode catalyst layer, a cellulose acetate electronic insulating layer and a cathode catalyst layer onto a single carbon fibre paper substrate. The single electrode supported DMFC has a total thickness of 3.88 × 10^?2 cm and showed a 104% improvement in volumetric specific power density over a two electrode DMFC configuration under passive conditions at ambient temperature and pressure (1 atm, 25 °C).     

Infiltrated Sr2Fe1.5Mo0.5O6/La0.9Sr0.1Ga0.8Mg0.2O3 electrodes towards high performance symmetrical solid oxide fuel cells fabricated by an ultra-fast and time-saving procedure

Herein, the Sr₂Fe_1.5Mo_0.5O₆ (SFM) precursor solution is infiltrated into a tri-layered “porous La_0.9Sr_0.1Ga_0.8Mg_0.2O₃ (LSGM)/dense LSGM/porous LSGM” skeleton to form both SFM/LSGM symmetrical fuel cells and functional fuel cells by adopting an ultra-fast and time-saving procedure. The heating/cooling rate when fabricating is fixed at 200 °C/min. Thanks to the unique cell structure with high thermal shock resistance and matched thermal expansion coefficients (TEC) between SFM and LSGM, no SFM/LSGM interfacial detachment is detected. The polarization resistances (Rp) of SFM/LSGM composite cathode and anode at 650 °C are 0.27 Ω·cm² and 0.235 Ω·cm², respectively. These values are even smaller than those of the cells fabricated with traditional method. From scanning electron microscope (SEM), a more homogenous distribution of SFM is identified in the ultra-fast fabricated SFM/LSGM composite, therefore leading to the enhanced performance. This study also strengthens the evidence that SFM can be used as high performance symmetrical electrode material both running in H₂ and CH₄. When using H₂ as fuel, the maximum power density of “SFM-LSGM/LSGM/LSGM-SFM” functional fuel cell at 700 °C is 880 mW cm^− 2. By using CH₄ as fuel, the maximum power densities at 850 and 900 °C are 146 and 306 mW cm^− 2, respectively.     

A novel single phase cathode material for a proton-conducting SOFC

A novel single phase BaCe_0.5Bi_0.5O_3 ? δ (BCB) was employed as a cathode material for a proton-conducting solid oxide fuel cell (SOFC). The single cell, consisting of a BaZr_0.1Ce_0.7Y_0.2O_3 ? δ (BZCY7)-NiO anode substrate, a BZCY7 anode functional layer, a BZCY7 electrolyte membrane and a BCB cathode layer, was assembled and tested from 600 to 700 °C with humidified hydrogen (～3% H₂O) as the fuel and the static air as the oxidant. An open-circuit potential of 0.96 V and a maximum power density of 321 mW cm^?2 were obtained for the single cell. A relatively low interfacial polarization resistance of 0.28Ω cm² at 700 °C indicated that the BCB was a promising cathode material for proton-conducting SOFCs.     

Electrochemical performance of a novel CoTETA/C catalyst for the oxygen reduction reaction

In this communication, we report a novel CoTETA/C catalyst for the oxygen reduction reaction (ORR) which was prepared from a carbon-supported cobalt triethylenetetramine chelate, followed by heat treatment in an inert atmosphere. Electrochemical performances were measured using rotating disk electrode (RDE) technique and a PEM fuel cell test station. For a H₂–O₂ fuel cell system, the maximum output power density reached 162 mW cm^?2 at 25 °C with non-humidified reaction gases. We found a nanometallic face-centered cubic (fcc) α-Co phase embedded in the graphitic carbon after pyrolysis, based on X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) measurements. These results indicated that CoTETA/C is a promising catalyst for the ORR.     

Enhanced performance of an anode-supported YSZ thin electrolyte fuel cell with a laser-deposited Sm0.2Ce0.8O1.9 interlayer

A power density of over 1.4 W cm^?2 at 0.7 V was achieved at 750 °C for an anode-supported YSZ thin electrolyte fuel cell with a dense Sm_0.2Ce_0.8O_1.9 (SDC) interlayer fabricated by pulsed laser deposition, while the cell with a conventional porous SDC interlayer exhibited only 0.8 W cm^?2 at this voltage. The dense SDC interlayer significantly reduced the ohmic resistance of the fuel cell. For example, at 750 °C, the ohmic resistance of the fuel cell with a dense SDC interlayer was 0.08 Ω cm²; while that of the cell with a porous SDC interlayer fabricated by conventional screen-printing was 0.16 Ω cm². The pronounced reduction in ohmic resistance might be due to the fully dense structure and thus improved electrical conductivity of the SDC interlayer, increased contact area at the interface between the dense SDC interlayer and the YSZ electrolyte, and suppressed Zr migration into the SDC interlayer.     

Formation of porous TiOx biomaterials in H3PO4 electrolytes

In this work, formation of porous TiO_x layers and theirs corrosion behavior were studied. Application of H₃PO₄ electrolytes results in porous TiO_x formation. The process is enhanced by small amount of HF content in the electrolyte. The HF results in higher current density, enhancing dissolution. Small 0.5% HF concentration results in nanopores formation, with pore diameter of about 45 nm. Increase of HF concentration up to 10% results in pores with average diameter of about 5.2 μm. An increase of etching time results in larger pore diameter, but between large 2–5 μm diameter pores smallest ones were observed with diameter below 200 nm. In the initial etching process a remnants of the flat surface are presents with initial cracks in the surface, indicating places for growth of the pores.The TiO_x layers can be used as a biomaterial. The corrosion behavior of the layer investigated in Ringer’s solution, revealed an excellent corrosion resistance, with respect to pure Ti.     

A completely spray-coated membrane electrode assembly

We present a proton exchange membrane fuel cell (PEMFC) manufacturing route, in which a thin layer of polymer electrolyte solution is spray-coated on top of gas diffusion electrodes (GDEs) to work as a proton exchange membrane. Without the need for a pre-made membrane foil, this allows inexpensive, fast, large-scale fabrication of membrane-electrode assemblies (MEAs), with a spray-coater comprising the sole manufacturing device. In this work, a catalyst layer and a membrane layer are consecutively sprayed onto a fibrous gas diffusion layer with applied microporous layer as substrate. A fuel cell is then assembled by stacking anode and cathode half-cells with the membrane layers facing each other. The resultant fuel cell with a low catalyst loading of 0.1 mg Pt/cm² on each anode and cathode side is tested with pure H₂ and O₂ supply at 80 °C cell temperature and 92% relative humidity at atmospheric pressure. The obtained peak power density is 1.29 W/cm² at a current density of 3.25 A/cm². By comparison, a lower peak power density of 0.93 W/cm² at 2.2 A/cm² is found for a Nafion NR211 catalyst coated membrane (CCM) reference, although equally thick membrane layers (approx. 25 μm), and identical catalyst layers and gas diffusion media were used. The superior performance of the fuel cell with spray-coated membrane can be explained by a decreased low frequency (mass transport) resistance, especially at high current densities, as determined by electrochemical impedance spectroscopy.     

A novel process to prepare porous membranes comprising SnO2 nanoparticles and P(MMA-AN) as polymer electrolyte

We have successfully developed a new process to prepare porous poly(methyl methacrylate-co-acrylonitrile) (P(MMA-AN)) copolymer based gel electrolyte. The porous structure in the polymer matrix is achieved by adding SnO₂ nanoparticles which are mostly used as gas sensor materials. The quasi-aromatic solvent, NMP, has an electron-repulsion effect with the space charge layer on the surface of SnO₂ nanoparticles and forms a special gas–liquid phase interface. Once the cast polymer solution is stored at an elevated temperature to evaporate the solvent, gas–liquid phase separation happens and spherical pores are obtained. The ionic conductivity at room temperature of the prepared gel polymer electrolyte based on the porous membrane is as high as 1.54 × 10⁻³ S cm⁻¹ with the electrochemical stability up to 5.10 V (vs. Li/Li⁺). This method presents another promising way to prepare porous polymer electrolyte for practical use.     

Enhancement of the performances of a single concentric glucose/O2 biofuel cell by combination of bilirubin oxidase/Nafion cathode and Au–Pt anode

This work deals with a novel preparation method of bilirubin oxidase/2,2′-azinobis-3-ethylbenzothiazoline-6-sulfonic acid electrode. The enzyme and its mediator were adsorbed on carbon Vulcan XC-72R before their immobilization into a Nafion^® matrix. Promising results were obtained when this biocathode was associated with Au₇₀Pt₃₀ nanoparticles as anode in a single concentric glucose/O₂ biofuel cell (BFC). The latter BFC delivered at 37 °C a power density of 90 μW cm^?2 for a cell voltage of 0.4 V in phosphate buffer (pH 7.4) containing 0.01 M glucose. Moreover, the electrical performances were increased with the concentration of glucose by generating up to 190 μW cm^?2 for a cell voltage of 0.52 V when the concentration of the renewable fuel reached 0.7 M.     

Preparation process for improving cathode electrode structure in direct methanol fuel cell

The cathode electrode structure of the direct methanol fuel cell (DMFC) was improved by a novel catalyst ink preparation method. Regulation of the solvent polarity in the cathode catalyst ink caused increases in the electrochemical active surface (EAS) for the oxygen reduction reaction (ORR) as well as decreases in the methanol crossover effect. In a two-step preparation, agglomerates consisting of catalyst and Nafion ionomers were decreased in size, and polar groups in the ionomers formed organized networks in the cathode catalyst layer. Despite Pt catalysts in the cathode being only 0.5 mg cm^? 2, the maximum power density of the improved membrane electrode assembly (MEA) was 120 mW cm^? 2, at 3 M methanol, which was much larger than that of traditional MEA (67 mW cm^? 2).     

Mechanoelectrochemical synthesis and properties of porous nano-Ti–6Al–4V alloy with hydroxyapatite layer for biomedical applications

Formation of porous morphology in nanocrystalline mechanically alloyed and electrochemically etched Ti–6Al–4V biomedical alloy was investigated. The alloy was electrochemically etched in a mixture of H₃PO₄ and HF. The electrochemical etching results in broad range from micro(nano)-macropores formation in the surface layer, with diameter in the range of 3 nm–60 µm. On the etched surface hydroxyapatite was electrochemically deposited by using 0.042 M Ca(NO₃)₂ + 0.025 (NH₄)₂HPO₄ + 0.1M HCl electrolyte. In this way bioactive surface was prepared. The pores in the surface acts as anchors for the hydroxyapatite, which grows inside them. Due to the porous morphology, the etched as well as HA deposited surface is promising for hard tissue implant applications. The nanocrystalline alloy has a nanohardness and Young modulus in the range of 993–1275 HV and 137–162 GPa, respectively.     

A glucose/O2 biofuel cell base on nanographene platelet-modified electrodes

This study demonstrated a novel nanographene platelets (NGPs)-based glucose/O₂ biofuel cell (BFC) with the glucose oxidase (GOD) as the anodic biocatalysts and the laccase as the cathodic biocatalysts. The GOD/NGPs-modified electrode exhibited good catalytic activity towards glucose oxidation and the laccase/NGPs-modified electrode exhibited good catalytic activity towards O₂ electroreduction. The maximum power density was ca. 57.8 μW cm^? 2 for the assembled glucose/O₂ NGPs-based BFC. These results indicated that the NGPs were very useful for the future development of novel carbon-based nanomaterials BFC device.     

Iodinated carbon materials for oxygen reduction reaction in proton exchange membrane fuel cell. Scalable synthesis and electrochemical performances

Doped graphene-based cathode catalysts are considered as promising competitors for ORR, but their power density has been low compared to Pt-based cathodes, mainly due to poor mass-transport properties. A new electrocatalyst for PEMFCs, an iodine doped grahene was prepared, characterized, and tested and the results are presented in this paper. We report a hybrid derived electrocatalyst with increased electrochemical active area and enhanced mass-transport properties. The electrochemical performances of several configurations were tested and compared with a typical Pt/C cathode configuration. As a standalone catalyst, the iodine doped graphene gives a performance with 60% lower than if it is placed between gas diffusion layer and catalyst layer. If it is included as microporous layer, the electrochemical performances of the fuel cell are with 15% bigger in terms of power density than the typical fuel cell with the same Pt/C loading, proving the beneficial effect of the iodine doped graphene for the fuel cell in the ohmic and mass transfer region. Moreover, the hybrid cathode manufactured by commercial Pt/C together with the material with best proprieties, is tested in a H₂-Air fuel cell and a power density of 0.55 W cm⁻² at 0.52 V was obtained, which is superior to that of a commercial Pt-based cathode tested under identical conditions (0.46 W cm⁻²).     

Preparation of an extremely dense BaCe0.8Sm0.2O3−δ thin membrane based on an in situ reaction

The thin membrane of BaCe_0.8Sm_0.2O_3−δ (BCS) with high quality was successfully fabricated on porous NiO–BCS anode substrate through a novel in situ reaction method. The key part of this method is to directly spray well-mixed suspension of BaCO₃, CeO₂ and Sm₂O₃ instead of pre-synthesized BCS ceramic powder on the anode substrate. After sintering at 1400 °C for 5 h, the extremely dense electrolyte membrane in the thickness of 10 μm is obtained. A single cell was assembled with La_0.7Sr_0.3FeO_3−σ as cathode and tested with humidified hydrogen as fuel at 650 °C. The open circuit voltage (OCV) and maximum power density respectively reach 1.04 V and 535 mW/cm². Interface resistance of cell under open circuit condition was also investigated.     

Methane-fueled SOFC with traditional nickel-based anode by applying Ni/Al2O3 as a dual-functional layer

Novel γ-Al₂O₃ supported nickel (Ni/Al₂O₃) catalyst was developed as a functional layer for Ni–ScSZ cermet anode operating on methane fuel. Catalytic tests demonstrated Ni/Al₂O₃ had high and comparable activity to Ru–CeO₂ and much higher activity than the Ni–ScSZ cermet anode for partial oxidation, steam and CO₂ reforming of methane to syngas between 750 and 850 °C. By adopting Ni/Al₂O₃ as a catalyst layer, the fuel cell demonstrated a peak power density of 382 mW cm^?2 at 850 °C, more than two times that without the catalyst layer. The Ni/Al₂O₃ also functioned as a diffusion barrier layer to reduce the methane concentration within the anode; consequently, the operation stability was also greatly improved without coke deposition.     

Activity of Pt anode catalyst modified by underpotential deposited Pb in a direct formic acid fuel cell

We characterized the electrocatalytic activity of platinum electrode modified by underpotential deposited lead (PtPb_upd) for a formic acid (HCOOH) oxidation and investigated the influence on the power performance of direct formic acid fuel cells (DFAFC). Based on the electrochemical analysis using cyclic voltammetry and chronoamperometry, PtPb_upd electrode modified by underpotential deposition (UPD) exhibited significantly enhanced catalytic activity for HCOOH oxidation below anodic overpotential of 0.4 V (vs. SCE). Multi-layered PtPb_upd electrode structure of Pt/Pb_upd/Pt resulted in more stable and enhanced performance using 50% reduced loading of anode catalyst. The performance of multi-layered PtPb_upd anode is about 120 mW/cm² at 0.4 V and it also showed a sustainable cell activity of 0.52 V at an application of constant current loading of 110 mA/cm².     

A direct borohydride–peroxide fuel cell using a Pd/Ir alloy coated microfibrous carbon cathode

A direct borohydride fuel cell with a Pd/Ir catalysed microfibrous carbon cathode and a gold-catalysed microporous carbon cloth anode is reported. The fuel and oxidant were NaBH₄ and H₂O₂, at concentrations within the range of 0.1–2.0 mol dm⁻³ and 0.05–0.45 mol dm⁻³, respectively. Different combinations of these reactants were examined at 10, 25 and 42 °C. At constant current density between 0 and 113 mA cm⁻², the Pd/Ir coated microfibrous carbon electrode proved more active for the reduction of peroxide ion than a platinised-carbon one. The maximum power density achieved was 78 mW cm⁻² at a current density of 71 mA cm⁻² and a cell voltage of 1.09 V.     

Development of micro-tubular SOFCs with an improved performance via nano-Ag impregnation for intermediate temperature operation

Micro-tubular solid-oxide fuel cell consisting of a 10-μm thick (ZrO₂)_0.89(Sc₂O₃)_0.1(CeO₂)_0.01 (ScSZ) electrolyte on a support NiO/(ScSZ) anode (1.8 mm diameter, 200 μm wall thickness) with a Ce_0.8Gd_0.2O_1.9 (GDC) buffer-layer and a La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ (LSCF)/GDC functional cathode has been developed for intermediate temperature operation. The functional cathode was in situ formed by impregnating the well-dispersed nano-Ag particles into the porous LSCF/GDC layer using a citrate method. The cells yielded maximum power densities of 1.06 W cm⁻² (1.43 A cm⁻², 0.74 V), 0.98 W cm⁻² (1.78 A cm⁻², 0.55 V) and 0.49 W cm⁻² (1.44 A cm⁻², 0.34 V), at 650, 600 and 550 °C, respectively.     

Cost-effective solid oxide fuel cell prepared by single step co-press-firing process with lithiated NiO cathode

A cost-effective cell fabrication process was developed for intermediate temperature solid oxide fuel cells (IT-SOFCs). Co-doped ceria Ce_0.8Gd_0.05Y_0.15O_1.9 (GYDC) was synthesized by carbonate co-precipitation method. Lithiated NiO was prepared by glycine-nitrate combustion method and adopted as cathode material for IT-SOFCs. Single cell was fabricated by one-step dry-pressing and co-firing anode, anode functional layer (AFL), electrolyte and cathode together at 1200 °C for 4 h. The cell presented decent performance and an overall electrode polarization resistance of 0.54 Ω cm² has been achieved at 600 °C. These results demonstrate the possibility of using lithiated NiO as cathode material for ceria-based IT-SOFCs and the development of affordable fuel cell devices is encouraged.