Characterization of the 75% Gd0.8Sr0.2CoO3−δ/25% Ce0.9Gd0.1O2−δ composite cathode system for use in intermediate temperature solid oxide fuel cells

The composite cathode system is examined for suitability on a Ce_0.9Gd_0.1O_2−δ electrolyte based solid oxide fuel cell at intermediate temperatures (500–700 °C). The cathode is characterized for electronic conductivity and area specific charge transfer resistance. This cathode system is chosen for its excellent thermal expansion match to the electrolyte, its relatively high conductivity (115 S cm⁻¹ at 700 °C), and its low activation energy for oxygen reduction (99 kJ mol⁻¹). It is found that the decrease of sintering temperature of the composite cathode system produces a significant decrease in charge transfer resistances to as low as 0.25 Ω cm². The conductivity of the cathode systems is between 40 and 88 S cm⁻¹ for open porosities of 30–40%.     

An alkaline direct NaBH4–H2O2 fuel cell with high power density

A high performance alkaline direct borohydride–hydrogen peroxide fuel cell with Pt–Ru catalyzed nickel foam as anode and Pd–Ir catalyzed nickel foam as cathode is reported. The electrodes were prepared by electrodeposition of the catalyst components on nickel foam. Their morphology and composition were analyzed by SEM–EDX. The effects of concentrations of NaBH₄ and H₂O₂ as well as operation temperature on the cell performance were investigated. The cell exhibited an open circuit voltage of about 1.0 V and a peak power density of 198 mW cm⁻² at a current density of 397 mA cm⁻² and a cell voltage of 0.5 V using 0.2 mol dm⁻³ NaBH₄ as fuel and 0.4 mol dm⁻³ H₂O₂ as oxidant operating at room temperature. Electrooxidation of NaBH₄ on Pt–Ru nanoparticles was studied using a rotating disk electrode and complete 8e⁻ oxidation was observed in 2 mol dm⁻³ NaOH solution containing 0.01 mol dm⁻³ NaBH₄.     

Enzymatic hydrogen production by light-sensitized anodized tubular TiO2 photoanode

Preliminary experiments with a slurry system of enzyme and powdery photocatalyst mixed in one compartment suggested that the electron transfer from light-sensitized photocatalyst to enzyme is the rate-determining step. Hence, in this study an anodized tubular TiO₂ electrode (ATTE) on a titanium substrate was examined as a photoanode in an anodic cell for enzymatic hydrogen production in a cathodic cell. Anodization of Ti foil in a two-electrode electrochemical cell followed by annealing in an O₂ atmosphere led to the formation of a tube-shaped TiO₂ arrays, destroyed tube arrays, or spongelike TiO₂ dense film. Samples were proven based on methylene blue (MB) discoloration to be photocatalytically active. The rate of photocatalytic hydrogen production in one of the samples (20 V–25 °C in a mixed electrolyte/350 °C–5 h) was 40 μmol/(h cm²) with a 0.1 M Na₂S electrolyte in one compartment reactor system, while the enzymatic hydrogen production rate with light-sensitized photoanode was 30 μmol/(h cm²) in the cathodic compartment with an oxygen production rate of 15 μmol/(h cm²) in the anodic compartment. These results confirmed the successful evolution of stoichiometric H₂ and O₂ separately. For the system with a sample (20 V–5 °C in 0.5% HF/650 °C–5 h), a hydrogen production rate was ca. 43 μmol/(h cm²) in the cathodic compartment and an oxygen production rate was ca. 20 μmol/(h cm²) in the anodic compartment. X-ray diffraction (XRD) results clearly indicated that the samples showing the highest evolution rate were composed of both anatase and rutile, while those made of either anatase or rutile showed a lower evolution rate. Higher annealing temperatures increased the thickness of the oxide barrier layer and obstructed the charge transfer to the back contact.     

Electrochromic properties of tungsten oxide nanowires fabricated by electrospinning method

In this work, we report electrochromic properties of polycrystalline WO₃ nanowire electrodes fabricated on an indium tin oxide (ITO)-coated substrate by electrospinning method. The electrochromic and electrical properties of the electrospun WO₃ nanowire electrodes are investigated and compared with those of conventional WO₃ thin film electrodes. As a result, the one-dimensional WO₃ nanowires show faster charge transfer and optical responses with a bleaching time of 1.0 s and a coloring time of 4.2 s than the thin film electrodes. The coloration efficiency of the electrospun WO₃ nanowires is also greater (56 cm²/C) by 21% than the thin film along with an improved memory effect after coloring process.     

La0.84Sr0.16MnO3−δ cathodes impregnated with Bi1.4Er0.6O3 for intermediate-temperature solid oxide fuel cells

La_0.84Sr_0.16MnO_3−δ–Bi_1.4Er_0.6O₃ (LSM–ESB) composite cathodes are fabricated by impregnating LSM electronic conducting matrix with the ion-conducting ESB for intermediate-temperature solid oxide fuel cells (IT-SOFCs). The performance of LSM–ESB cathodes is investigated at temperatures below 750 °C by AC impedance spectroscopy. The ion-impregnation of ESB significantly enhances the electrocatalytic activity of the LSM electrodes for the oxygen reduction reactions, and the ion-impregnated LSM–ESB composite cathodes show excellent performance. At 750 °C, the value of the cathode polarization resistance (R_p) is only 0.11 Ω cm² for an ion-impregnated LSM–ESB cathode, which also shows high stability during a period of 200 h. For the performance testing of single cells, the maximum power density is 0.74 W cm⁻² at 700 °C for a cell with the LSM–ESB cathode. The results demonstrate the ion-impregnated LSM–ESB is one of the promising cathode materials for intermediate-temperature solid oxide fuel cells.     

A high-performance counter electrode based on poly(3,4-alkylenedioxythiophene) for dye-sensitized solar cells

A poly(3,3-diethyl-3,4-dihydro-2H-thieno-[3,4-b][1,4]dioxepine) (PProDOT-Et₂) counter electrode prepared by electrochemical polymerization on a fluorine-doped tin oxide (FTO) glass substrate was incorporated in a platinum-free dye-sensitized solar cell (DSSC). The surface roughness and I⁻/I₃⁻ redox reaction behaviors based on PProDOT-Et₂, poly(3,4-propylenedioxythiophene) (PProDOT), poly(3,4-ethylenedioxythiophene) (PEDOT), and sputtered-Pt electrodes were characterized, and their performances as counter electrodes in DSSCs were compared. Cells fabricated with a PProDOT-Et₂ counter electrode showed a higher conversion efficiency of 7.88% compared to cells fabricated with PEDOT (3.93%), PProDOT (7.08%), and sputtered-Pt (7.77%) electrodes. This enhancement was attributed to increases in the effective surface area and good catalytic properties for I₃⁻ reduction. In terms of the film thickness effect, the fill factor was strongly dependent on the deposition charge capacity of the PProDOT-Et₂ layer, but the aggregation of PProDOT-Et₂ in thicker layers (>80 mC cm⁻²) resulted in decreases in J_SC and the cell conversion efficiency. The charge transfer resistances (R_ct1) of the PProDOT-Et₂ counter electrodes had the lowest value of ∼18 Ω at a deposition charge capacity of 40 mC cm⁻². These results indicate that films with high conductivity, high active surface area, and good catalytic properties for I₃⁻ reduction can potentially be used as the counter electrode in a high-performance DSSC.     

The effect of gas compositions on the performance and durability of solid oxide electrolysis cells

High-temperature electrolysis with various gas compositions has been performed to investigate the effects of the hydrogen partial pressure and the humidity generated by the steam electrode on the performance and durability of solid oxide electrolysis cells. The power density of the button cell used in this research is 0.48 W cm⁻² at 750 °C, and the flow rates of the air and humidified hydrogen are 100 cc min⁻¹. By changing the flow ratio of H₂:Ar:H₂O(g) from 10:0:4 to 1:9:4, the cell's OCV decreases from 0.973 V to 0.877 V, and the charge transfer resistance increases from 1.126 Ω cm² to 1.645 Ω cm². The close relationship between the conversion efficiency of high-temperature electrolysis and steam composition is evident in the increase in the cell's charge transfer resistance from 0.381 Ω cm² to 1.056 Ω cm² as the steam content changed from 40 vol% to 3 vol%. Although the electrochemical splitting of water is stimulated in the short term by excessive steam flow, the Ni-YSZ electrodes have been damaged by the steam electrode's low H₂ partial pressure. Consequently, the steam electrode's gas composition must be optimized in the long-term because of the trade-off between performance and durability, which depends on the water concentration of the steam electrodes.     

The photoinduced evolution of O2 and H2 from a WO3 aqueous suspension in the presence of Ce/Ce

This is a report on the production of O₂ and H₂ from photocatalytic and photochemical processes in the WO₃–H₂O–Ce⁴⁺_aq–hν system. The photoproduction of O₂ and H₂ was studied over the range of WO₃ concentrations from 2 to 8 g dm⁻³, and conduction band electron scavenger concentrations 1–20 mM Ce_aq⁴⁺. Medium and high concentrations of the electron scavenger gave mainly O₂ as the main product. Dilute solutions of [Ce_aq⁴⁺]< 2 mM initially produced dioxygen, and then hydrogen after an induction period of 3–4 h. Yields of 140–250 μmol O₂  h⁻¹ and 1–7 μmol H₂ h⁻¹ were obtained and were found to depend on the physical properties and content of WO₃, the concentration of the electron scavenger, illumination period and wavelength, and the radiation geometry. The photoactivity of the suspension was correlated to the level of crystallinity of WO₃ powders. The studied system utilizes WO₃ to accomplish the initial light absorption, charge separation, and production of O₂ and H⁺ from the interaction of water molecules with photogenerated WO₃ valence band holes, in the presence of Ce⁴⁺_aq species as a scavenger of conduction band electrons. This is followed by the evolution of H₂ from a homogeneous photochemical reduction of H⁺ and/or H₂O by photoexcited Ce³⁺_aq, formed from the earlier reduction of Ce⁴⁺_aq. The obtained results show that, with an appropriate design, tungsten trioxide is a promising material that can be used as a photoactive component in energy conversion systems or in environmental photocatalysis, using artificial or solar light.     

Behavior of single chambered mediatorless microbial fuel cell (MFC) at acidophilic, neutral and alkaline microenvironments during chemical wastewater treatment

Single chamber mediatorless microbial fuel cell (MFC; non-catalyzed graphite electrodes; open air cathode) behaviour was evaluated under different pH microenvironments [acidophilic (pH 6), neutral (pH 7) and alkaline (pH 8)] during chemical wastewater treatment employing anaerobic mixed consortia as anodic biocatalyst at room temperature (29 ± 2 °C). The performance was found to depend on the feed pH used. Higher current density was observed at acidophilic conditions [pH 6; 186.34 mA/m²; 100 Ω] compared to neutral [pH 7; 146.00 mA/m²; 100 Ω] and alkaline [pH 8; 135.23 mA/m²; 100 Ω]. On the contrary, substrate degradation was found to be effective at neutral pH conditions (ξ_COD – 58.98%; SDR – 0.67 kg COD/m³-day) followed by alkaline (ξ_COD – 55.76%; SDR – 0.62 kg COD/m³-day) and acidophilic (ξ_COD of 47.80%; SDR 0.58 kg COD/m³-day) conditions studied. However, relatively higher specific power yield was observed at acidophilic microenvironment (46 mW/kg COD_R) compared to neutral (35 mW/kg COD_R) and alkaline (34 mW/kg COD_R) conditions. The behaviour of the MFC was also evaluated employing electron discharge, cyclic voltammetry, cell potentials, Coulombic efficiency and sustainable power analysis. Acidophilic operation showed higher Coulombic efficiency and effective electron discharge at relatively higher resistance compared to neutral and alkaline conditions studied.     

Semiconductor-sensitized solar cells based on nanocrystalline In2S3/In2O3 thin film electrodes

A possibility of semiconductor-sensitized thin film solar cells have been proposed. Nanocrystalline In₂S₃-modified In₂O₃ electrodes were prepared with sulfidation of In₂O₃ thin film electrodes under H₂S atmosphere. The band gap (E_g) of In₂S₃ estimated from the onset of the absorption spectrum was approximately 2.0 eV. The photovoltaic properties of a photoelectrochemical solar cell based on In₂S₃/In₂O₃ thin film electrodes and I⁻/I₃⁻ redox electrolytes were investigated. This photoelectrochemical cell could convert visible light of 400–700 nm to electron. A highly efficient incident photon-to-electron conversion efficiency (IPCE) of 33% was obtained at 410 nm. The solar energy conversion efficiency, η, under AM 1.5 (100 mW cm⁻²) was 0.31% with a short-circuit photocurrent density (J_sc) of 3.10 mA cm⁻², a open-circuit photovoltage (V_oc) of 0.26 V, and a fill factor ( ff ) of 0.38.     

Performance of lanthanum strontium manganite electrodes at high pressure

The high-pressure performance of lanthanum strontium manganite (LSM), LSM-zirconia, and LSM/ceria composite electrodes was studied by impedance spectroscopy and dc methods. Electrode resistances decreased in proportion to P(O₂)^1/2 for the LSM electrode in both cathodic and anodic directions to at least 10 MPa (∼100 atm), a decrease that was attributed to dissociative oxygen adsorption and related phenomena. For the LSM-20/zirconia composite electrode, resistances decreased in proportion to P(O₂)^1/4 across the entire pressure range considered. Two principal features appeared in the impedance spectra, one that showed a P(O₂)^1/4 dependence attributed to charge transfer reactions, and a smaller feature that was nearly pressure-independent, possibly due to transport in the zirconia portion of the composite. For the LSM-20/ceria composite electrode, resistances decreased as P(O₂)^0.3-0.4 at high pressure, depending on temperature. Two features appeared in the impedance spectra: one at low to intermediate frequency having a ∼P(O₂)^1/2 dependence and a second at high frequency having a ∼P(O₂)^1/4 dependence. These features are attributed to dissociative oxygen adsorption and to charge transfer reactions, respectively. Results suggest that cathodic losses can be substantially lowered by operation of solid oxide fuel cells at greater than ambient pressure.     

Promotion of electrochromism in spray-deposited molybdenum oxide-doped iridium oxide thin films

Electrochromic molybdenum oxide-doped iridium oxide thin films were prepared by using a pneumatic spray pyrolysis technique onto fluorine-doped tin oxide (FTO) coated conducting glass substrates. An aqueous solution of 0.01 M ammonium molybdate was mixed with 0.01 M iridium trichloride in different volume proportions and the resultant solution was used as a precursor for spraying. An aqueous electrolyte (0.5 N H₂SO₄) was used to study electrochromic properties of thin films using cyclic voltammetry (CV), chronoamperometry (CA) and spectrophotometry. During the potential scan the iridium oxide electrode switches between coloured and bleached state due to Ir⁺⁴–Ir⁺³ intervalency charge transfers. The optical density difference (ΔOD)_λ=630 nm and colouration efficiency was maximum for 2% molybdenum oxide-doped sample. Moreover, loss in charge density during extended cycling is less than undoped and other doped (>2%) samples.     

Composite cathodes based on Sm0.5Sr0.5CoO3−δ with porous Gd-doped ceria barrier layers for solid oxide fuel cells

Cobaltite-based perovskites based on Sm_0.5Sr_0.5CoO_3−δ (SSC) are attractive as a cathode material with a barrier layer for solid oxide fuel cells (SOFC) due to their high electrochemical activity and electrical conductivity. SSC, synthesized by a complex method, is used as a cathode material in a composite cathode with Gd-doped ceria (GDC). A porous GDC layer is fabricated as a barrier to resist reactions of SSC with yttria-stabilized zirconia (YSZ). The effects of the ratio of SSC on GDC in composite cathodes and the thickness of the GDC barrier are characterized in this study. An SOFC with an SSC7–GDC3 composite cathode on a 4 μm GDC layer at 0.8 V yields the highest fuel cell performance: 1.24 W cm⁻² and 0.61 W cm⁻² at 780 °C and 680 °C, respectively. Impedance analysis indicates that the ohmic resistances are more dependent upon the GDC barrier thickness than the cathode composition. The polarization resistances at 780 °C and 730 °C exhibit similar values, but with decreasing temperature, the polarization resistances change dramatically according to the composition and barrier thickness. The ohmic and polarization resistances show different trends in different temperature ranges, due to the different charge transfer mechanisms of SSC and GDC within those temperature ranges. To obtain higher fuel cell performance, the addition of GDC into the porous SSC is effective, and the compositions of the composite cathode as well as the thickness of the barrier layer need to be optimized.     

First demonstration of photoelectrochemical water splitting by commercial W–Cu powder metallurgy parts converted to highly porous 3D WO3/W skeletons

Hydrogen evolution through photoelectrochemical (PEC) water splitting by tungsten oxide-based photoanodes, as a stable and environmental-friendly material with moderate band gap, has attracted significant interest in recent years. The performance of WO₃ photoanode could be hindered by its poor oxygen evolution reaction kinetics and high charge carrier recombination rate. Additionally, scalable and cost-effective commercial procedure to prepare nanostructured electrodes is still challenging. We present, for the first time, a novel and scalable method to fabricate highly efficient self-supported WO₃/W nanostructured photoanodes from commercial W–Cu powder metallurgy (P/M) parts for water splitting. The electrodes were prepared by electrochemical etching of Cu networks followed by hydrothermal growth of WO₃ nanoflakes. Interconnected channels of W skeleton provided high active surface area for the growth of WO₃ nanoflakes with a thickness of ~40 nm and lateral dimension of ~250 nm. The optimized photoelectrode having 35% interconnected porosity exhibited an impressive current density of 4.36 mA cm⁻² comprising a remarkable photocurrent of 1.71 mA cm⁻² at 1.23 V vs. RHE under 100 mW cm⁻² simulated sunlight. This achievement is amongst the highest reported photocurrents for WO₃ photoelectrodes with tungsten substrate reported so far. Impedance and Mott-Schottky analyses evidenced fast charge transfer, low recombination rate, and accelerated O₂ detachment provided by optimum 3D porous WO₃/W electrode. Due to the nature of the commercial P/M parts and low-temperature hydrothermal processing, the procedure is cost-effective and scalable which can pave a new route for the fabrication of highly porous and efficient water splitting electrodes.     

Improvement in the electrochemical performance of LixV2O5 induced by Tb doping

We have studied the electrochemical behavior of Tb_0.11V₂O₅ electrodes in propylene carbonate and LiClO₄. The techniques used in the study were cyclic voltammetry, discharge/charge polarization, FTIR and XRD. The Tb_0.11V₂O₅ compound was prepared using the xerogel route and the composite electrodes were membranes prepared with PVDF-binder and carbon. The results show that the Tb doping improves the electrochemical performance of V₂O₅ due to the bonding of the earth-rare ions and the residual H₂O in the V₂O₅ structure. The capacity fading was reduced, the specific reversible capacity was 330 mA g⁻¹ (C/4, cut-off 3.7–2.0 V) and the voltage presented a large plateau at 2.5 V for the Tb_0.11V₂O₅ electrodes. The charge transfer between Li and Tb_0.11V₂O₅ does not involve the oxidation–reduction of the Tb³⁺ ions.     

Experimental investigation on influences of methanol reformate impurities in performances of high temperature proton exchange membrane fuel cells

Even though the methanol reformate can be fed into the high temperature proton exchange membrane fuel cell, the influences of different reformate components on the fuel cell are still unclear. This work investigates the effects of CO, CO₂, H₂O, and CH₃OH in the fuel gas on the fuel cell performances. The distribution of relaxation times and equivalent circuit model are employed for analysis. The results show the increase of anodic charge and mass transfer resistances are main factors of CO poisoning which results in 77 mV overpotential. The maximum overpotential difference between CO₂ and Ar is only 4 mV, which means the dilution effect of CO₂ is similar to Ar. H₂O decreases the Ohmic and anodic charge transfer resistances and reducing the overpotential by 10 mV. CH₃OH below 3% has slight positive effect on the fuel cell performance. However, 5% CH₃OH results in high overpotential of 36 mV.     

Solid hybrid polyelectrolyte with high performance in electrochromic devices: Electrochemical stability and optical study

This paper presents a high-stability, single-phase hybrid polyelectrolyte (SPHP) applied in a large EC device (5×10 cm²) using WO₃ (electrochromic) and CeO₂–TiO₂ (counter-electrode–ion storage) electrodes, both produced by Leibniz—Institut of New Materials (Leibniz—INM, Germany). The electrochromic device exhibited excellent color and bleach reversibility, high coloration efficiency (>35 cm²/C) from the first cycle up to more than 60,000 CA cycles, and a maximum constant rate of deintercalation/intercalation (O_out/Q_in=1). Its remarkable behavior and high stability render this material an excellent candidate for application in electrochromic devices.     

Enhanced electrochemical stability of all-polymer redox supercapacitors with modified polypyrrole electrodes

Redox supercapacitors are attracting increasing attention as high power electrochemical sources and can either be coupled with batteries to provide peak power or replace batteries for memory back-up. In the present work, all-polymer solid-state supercapacitors with LiClO₄ and LiCF₃SO₃ doped polypyrrole electrodes and P(VDF-HFP)-PMMA based polymer gel electrolyte are fabricated. The polypyrrole electrodes are irradiated with 160 MeV Ni¹²⁺ ions at 5 × 10¹⁰, 5 × 10¹¹ and 5 × 10¹² ions cm⁻². A comparative study is made between unirradiated and irradiated supercapacitors with polypyrrole-based electrodes. An average capacitance of about 200 F gm⁻¹ is obtained. On successive charging and discharging, the capacitance decreases for supercapacitors with unirradiated electrodes but remains stable when irradiated electrodes are used. In addition, the capacitance is slightly decreased compared with that for unirradiated electrodes. Charge–discharge studies show a decrease in total charge–discharge time for supercapacitors with irradiated electrodes. The capacitance values calculated from cyclic voltammograms are higher than those determined from charge–discharge plots due to the added contribution of a leakage current. The coulombic efficiency of all the supercapacitors is about 90%.     

The effect of temperature on the charge transport and transient absorption properties of K27 sensitized DSSC

The charge transport and transient absorption properties of K27 dye-sensitized solar cell have been investigated. The current–voltage (I–V) characteristics of the solar cell were analyzed by the thermionic emission theory. The ideality factor, barrier height and series resistance values of the solar cell were determined. The ideality factor higher than unity indicated the presence of non-ideal behavior in current–voltage characteristics at lower voltages. At the higher voltages, the charge transport mechanism for the solar cell is controlled by a space-charge limited current (SCLC) with an exponential distribution of traps. The built potential values are determined from capacitance–voltage plot and were found to be 0.14 and 0.58 V, respectively. The transient absorption data of K27 DSSC device suggest that the fast and slow phases are taking place. While the fast phase corresponds to regeneration of the dye cation by the iodide redox couple, the slow phase corresponds to the decay of long-lived I₂⁻/ TiO₂ electron absorption. The best conversion efficiency for K27 DSSC was found to be 0.317% under 100 mW/cm² (FF=0.584, V_oc=480 mV, I_sc=1.131 mA). The photocurrent results indicate that the photogeneration of charge carriers is a monophotonic process.     

Electrochromic properties of heat-treated thin films of CeO2–TiO2–ZrO2 prepared by sol–gel route

CeO₂–TiO₂–ZrO₂ thin films were prepared using the sol–gel process and deposited on glass and ITO-coated glass substrates via dip-coating technique. The samples were heat treated between 100 and 500 °C. The heat treatment effects on the electrochromic performances of the films were determined by means of cyclic voltammetry measurements. The structural behavior of the film was characterized by atomic force microscopy and X-ray diffraction. Refractive index, extinction coefficient, and thickness of the films were determined in the 350–1000 nm wavelength, using nkd spectrophotometry analysis.Heat treatment temperature affects the electrochromic, optical, and structural properties of the film. The charge density of the samples increased from 8.8 to 14.8 mC/cm², with increasing heat-treatment temperatures from 100 to 500 °C. It was determined that the highest ratio between anodic and cathodic charge takes place with increase of temperature up to 500 °C.