RuO2 supported on Sb-doped SnO2 nanoparticles for polymer electrolyte membrane water electrolysers

With a colloid method, RuO₂ was deposited on Sb-doped SnO₂ nanoparticles (ATO, Aldrich, 30-40 nm), which was employed as a novel support material for anode catalysts of polymer electrolyte membrane water electrolysers (PEMWE). Distinctive RuO₂ nanoparticles (10-15 nm) were stably deposited on ATO nanoparticles, which were characterized with XRD and SEM. RuO₂/ATO exhibited higher activity than unsupported RuO₂ for oxygen evolution. A PEMWE single cell with 10 mg cm⁻² 20 wt.% RuO₂/ATO achieved 1.56 V at 1 A cm⁻² at 80 °C.     

Evaluation of MEA manufacturing parameters using EIS for SO2 electrolysis

Membrane electrode assembly (MEA) manufacturing parameters such as hot pressing pressure and pressing time were investigated for the use in a SO₂ electrolyser. The SO₂ electrolysis was optimised in terms of cell temperature, membrane thickness and catalyst loading. The electrolysis efficiency was evaluated using polarisation curves while electrochemical impedance spectroscopy (EIS) was used to determine the membrane resistance, activation energy and mass transport limitations. An electrical circuit, which included inductance, ohmic resistance, charge transfer, constant phase and Warburg elements, was used to fit the experimental data. The optimum hot pressing conditions were 50 kg cm⁻² for 5 min at 120 °C. Increased cell temperature (80 °C) resulted in a reduction of mass transport, while thicker membranes resulted in an increased mass transport due to lower water transport through the membrane. Increased catalyst loading (from 0.3 to 1 mgPtC.cm⁻²) improved the cell performance due to improved kinetics confirmed by the EIS data.     

The performance of Pt nanoparticles supported on Sb2O5.SnO2, on carbon and on physical mixtures of Sb2O5.SnO2 and carbon for ethanol electro-oxidation

Pt nanoparticles were supported on Sb₂O₅.SnO₂ (ATO), on carbon and on physical mixtures of ATO and carbon by an alcohol-reduction process using ethylene glycol as reducing agent. The obtained materials were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Their performance for ethanol oxidation was investigated at room temperature by chronoamperometry and in a direct ethanol fuel cell (DEFC) at 100 °C. Pt nanoparticles supported on a physical mixture of ATO and carbon showed a significant increase of performance for ethanol oxidation compared to Pt nanoparticles supported on ATO or on carbon.     

A hybridized electron-selective layer using Sb-doped SnO2 nanowires for efficient inverted polymer solar cells

We developed a novel hybridized electron-selective layer comprised of Sb-doped SnO₂ nanowires for efficient inverted polymer solar cells. A device containing Sb-doped SnO₂ nanowires with 0.1 mg/ml concentration showed a significant increase in power conversion efficiency to 3.23% with an enhanced fill factor, compared to a reference device without the nanowires (2.89%). Such improvement is attributed to the high electrical conductivity of one-dimensional Sb-doped SnO₂ nanowires and to the good light transmittance through the wide band gap of tin oxide. Also the surface morphology of the hybridized electron-selective layer is made denser and improved by incorporating one-dimensional Sb-doped SnO₂ nanowires, resulting in the enhancement of the photovoltaic performance.     

Formation of ultrafast-switching viologen-anchored TiO2 electrochromic device by introducing Sb-doped SnO2 nanoparticles

Ultrafast-switching viologen-anchored TiO₂ electrochromic device (ECD) was developed by introducing Sb-doped SnO₂ (Sb_xSn_1−xO₂, ATO) as counter electrode (CE), and the switching behavior of the fabricated ECD was investigated as a function of Sb-doping concentration. About 9-nm-sized Sb_xSn_1−xO₂ (x=0–0.3) nanoparticles were synthesized by a solvothermal reaction of tin (IV) chloride and antimony (III) chloride at 240 °C, and employed to fabricate 2.4-μm-thick transparent CE. Working electrode (WE) was formed from the 7-nm-sized TiO₂ nanoparticle by a doctor blade method, and the thickness of the nanoporous TiO₂ electrode was 4.5 μm. The phosphonated viologen, bis(2-phosphonylethyl)-4,4′-bipyridinium dibromide, was then adsorbed on the prepared films for the construction of the ECD. The response time was strongly dependent on the doping concentration of Sb in ATO, and the fastest switching response was observed at 3 mol%. At this composition, the coloration time was 5.7 ms, and the bleaching time was 14.4 ms, which is regarded as one of the best results so far reported.     

Nano-grain SnO2 electrodes for high conversion efficiency SnO2-DSSC

The nano-grain ZnO/SnO₂ composite electrode was prepared by adding 5 w% of the 200-250 nm ZnO particles to the 5 nm SnO₂ colloid in the presence of hydroxypropylcellulose (M.W.=80,000). The nano-grain SnO₂ electrode was obtained by removing the ZnO particles from the composite electrode using acetic acid. The FE-SEM micrographs revealed that both electrodes consisted of interconnected nano-grains that were ca. 800 nm in size, and the large pores between the grains furnished the wide electrolyte diffusion channels within the electrodes. The photovoltaic properties of the nano-grain electrodes were investigated by measuring the I-V behaviors, the IPCE spectra and the ac-impedance spectra. The nano-grain electrodes exhibited remarkably improved conversion efficiencies of 3.96% for the composite and 2.98% for the SnO₂ electrode compared to the value of 1.66% for the usual nano-particle SnO₂ electrode. The improvement conversion efficiencies were mainly attributed to the formation of nano-grains, which facilitated the electron diffusion within the grains. The improved electrolyte diffusion as well as the light-scattering effects enhanced the photovoltaic performance of the SnO₂ electrode.     

CO2 reduction in a solid oxide electrolysis cell with a ceramic composite cathode: Effect of load and thermal cycling

A solid oxide electrolysis cell (SOEC) powered by a renewable source can convert CO₂ into carbon monoxide, which is a valuable feedstock for a range of fuels and chemical processes. The cathode material of the SOEC is required to possess sufficient catalytic activity for CO₂ reduction, and also sustain the thermal and electrical load cycling to which the SOEC would be subjected when coupled with an intermittent renewable source without an auxiliary electricity or thermal storage system. The operating conditions can become even more challenging if solar or waste heat from exothermic downstream industrial processes is to be embedded in the process. In this study, we evaluated a mixed ionic–electronic conducting composite (La_0·80Sr_0.20Sc_0.05Mn_0·95O_3-δ–Gd_0.20Ce_0·80O_1.95) material as an SOEC cathode. Along with initial electrochemical performance, we investigated the cell's response to accelerated ageing tests, including electrical load cycling and extreme thermal cycling. Factors leading to performance degradation were studied by electrochemical impedance spectroscopy and structural characterisation of the cathode before and after the test. Thermal cycling resulted in more pronounced effect on the cell degradation rate as compared to electrical load cycling.     

Fabrication and characterization of nanostructured Ni–IrO2 electrodes for water electrolysis

Nanostructured Ni–IrO₂ electrodes were fabricated by electrodeposition in a two-step procedure: first arrays of nickel nanowires (NWs) were electrodeposited within pores of polycarbonate (PC) membranes, then iridium oxide nanoparticles were deposited on the Ni metal after membrane dissolution, for improving the catalytic activity. The aim was to compare performance of these electrodes with traditional ones consisting of Ni film. Different methods of deposition of the IrO₂ electrocatalyst were investigated and the effect on electrodes stability and activity is discussed. Despite a low coverage of Ni NWs by the electrocatalyst, results indicate a faster kinetics of O₂ evolution in 1 M KOH solution and an improvement of performances for electrolysers having a nanostructured anode.     

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%.     

Electrochemical reduction of CO2 in solid oxide electrolysis cells

This paper describes results on the electrochemical reduction of carbon dioxide using the same device as the typical planar nickel-YSZ cermet electrode supported solid oxide fuel cells (H₂-CO₂, Ni-YSZ|YSZ|LSCF-GDC, LSCF, air). Operation in both the fuel cell and the electrolysis mode indicates that the electrodes could work reversibly for the charge transfer processes. An electrolysis current density of ≈1 A cm⁻² is observed at 800 °C and 1.3 V for an inlet mixtures of 25% H₂-75% CO₂. Mass spectra measurement suggests that the nickel-YSZ cermet electrode is highly effective for reduction of CO₂ to CO. Analysis of the gas transport in the porous electrode and the adsorption/desorption process over the nickel surface indicates that the cathodic reactions are probably dominated by the reduction of steam to hydrogen, whereas carbon monoxide is mainly produced via the reverse water gas shift reaction.     

Preparation and study of IrO2/SiC-Si supported anode catalyst for high temperature PEM steam electrolysers

A novel catalyst material for oxygen evolution electrodes was prepared and characterised by different techniques. IrO₂ supported on a SiC-Si composite was synthesised by the Adams fusion method. XRD and nitrogen adsorption experiments showed an influence of the support on the surface properties of the IrO₂ particles, affecting the IrO₂ particle size. The prepared catalysts were electrochemically characterised by cyclic voltammetry experiments at 25,80,120 and 150 °C. In accordance with the observed variation in particle size, a support loading of up to 20% improved the activity of the catalyst. Powder conductivity measurements were also performed, which showed the influence of the support particles in the packing of IrO₂ particles, perhaps favouring the formation of channels and pores between particles, thus increasing the catalyst utilisation.     

Non-conductive TiO2 as the anode catalyst support for PEM water electrolysis

The applicability of a non-conductive TiO₂ as the support of the anodic catalyst for PEM water electrolysis was tested. Three TiO₂ samples with different specific surface areas were modified by IrO₂ using a modified version of the Adams fusion method. A constant weight ratio of IrO₂/TiO₂ of 0.6 was maintained in all cases. The size, specific surface area and morphology of IrO₂ electrocatalyst crystallites were investigated by X-ray diffraction, nitrogen adsorption (BET) and scanning electron microscopy, respectively. The electron conductivity of compressed catalyst powders was evaluated. Their electrochemical properties were studied on a rotating disk electrode (RDE) and finally in a laboratory electrolyser. Utilization of the TiO₂ support resulted in a reduction in the size of the IrO₂ crystallites. It was found that the lower the specific surface area of the supports, the higher was the electrochemical activity of the catalyst. This is most likely due to the formation of a conductive IrO₂ film on the surface of non-conductive supports. For the supports with a higher surface area, the amount of IrO₂ used was not sufficient to form an adequately compact film. This resulted in high electron resistance of such a catalyst. The RDE results were confirmed by a laboratory electrolysis test. Taken together with the excellent stability of TiO₂ in an anodic environment, these results suggest that these materials are promising supports if the appropriate amount of iridium is deposited.     

Conductive performances of solid polymer electrolyte films based on PVB/LiClO4 plasticized by PEG200, PEG400 and PEG600

Solid polymer electrolyte (SPE) films consisting of polyvinyl butyral (PVB) as host polymer, LiClO₄ as alkali salt at mole ratio of [O]:[Li] = 8, and different molecular weight polyethylene glycol (PEG) including PEG₂₀₀, PEG₄₀₀, and PEG₆₀₀ as plasticizers are prepared by physical blending method. The dielectric relaxation and electrochemical impedance measurements reveal that the conductive performances are improved by adding PEG as plasticizers through the enhancement in the moving space for ions, and PEG₄₀₀ performs plasticizing effect superior to PEG₂₀₀ and PEG₆₀₀. Their conductivity is measured by using a sandwiched Pt/SPE/Pt cell model. SPE with 30% PEG₄₀₀ (wt%) of PVB exhibits the maximum conductivity at room temperature, and its conductivity increases linearly with temperatures from 303 to 333 K at two to three orders of magnitude higher than that of the other two SPEs containing 30% PEG₂₀₀ and 30% PEG₆₀₀, respectively. However, their conductivity does not increase linearly with the increase in heating temperatures until the temperature reaches around 333 K; the decrease in conductivity with heating from their maxima is attributed to the restriction of ion moving space because of the crosslinking reaction between hydroxyl and aldehyde groups. As observed from the XRD and the microscopy results, PEG₄₀₀ is more effective than others in enhancing the conductive performances of these SPEs through changing LiClO₄ from crystalline to amorphous state, increasing the flexibility of PVB, disturbing the short distance sequential order of PVB chains, and promoting the formation of ‘pathway’ for ions’ movement.     

Effect of treatment temperature on the performance of RuO2 anode electrocatalyst for high temperature proton exchange membrane water electrolysers

Ruthenium oxide catalysts were prepared by a sol–gel technique and calcined at different temperatures e.g., 400 °C, 500 °C and 600 °C. The catalysts performance for the oxygen evolution reaction was studied using cyclic voltammetry and their performance in a high temperature proton exchange membrane water electrolyser (PEMWE) examined. Physio-chemical characterization was carried out to study the thermal stability, oxygen-metal bond formation, crystallinity phase and crystallite size, particle size and elemental analysis by TGA, FTIR, XRD, TEM and EDX respectively. The electrolyte used for electrochemical characterisation was 1.0 M H₃PO₄ and 0.5 M H₂SO₄. Additionally, the effect of calcination and electrolyte temperature on oxygen evolution reaction of RuO₂ catalysts was studied and the apparent activation energy was determined using chronoamperometry. The prepared RuO₂ were tested as anode catalyst in PEMWE in the temperature range of 120–150 °C using phosphoric acid doped polybenzimidazole membrane electrolyte. The physio-chemical and electrochemical characterization results indicate that RuO₂ calcined at 500 °C gave the best performance with a current density of 0.875 A cm⁻² at 1.8 V in a PEMWE operated at 150 °C.     

Effects of SnO2 on hydrogen desorption of MgH2

The hydrogen desorption properties of Magnesium Hydride (MgH₂) ball milled with cassiterite (SnO₂) have been investigated by X-ray powder diffraction and thermal analysis. Milling of pure MgH₂ leads to a reduction of the desorption temperature (up to 60 K) and of the activation energy, but also to a reduction of the quantity of desorbed hydrogen, referred to the total MgH₂ present, from 7.8 down to 4.4 wt%. SnO₂ addition preserves the beneficial effects of grinding on the desorption kinetics and limits the decrease of desorbed hydrogen. Best tradeoff – activation energy lowered from 175 to 148 kJ/mol and desorbed hydrogen, referred to the total MgH₂ present, lowered from 7.8 to 6.8 wt% – was obtained by co-milling MgH₂ with 20 wt% SnO₂.     

Enhanced CO2 stability of oxyanion doped Ba2In2O5 systems co-doped with La, Zr

In the solid oxide fuel cell (SOFC) field, proton conducting perovskite electrolytes offer many potential benefits. However, an issue with these electrolytes is their stability at elevated temperatures in the presence of CO₂. Recently we have reported enhanced oxide ion/proton conductivity in oxyanion (silicate, phosphate) doped Ba₂In₂O₅, and in this paper we extend this work to examine the stability at elevated temperatures towards CO₂. The results show improved CO₂ stability compared to the undoped system, and moreover this can be further improved by co-doping on either the Ba site with La, or the In site with Zr. While this co-doping strategy does reduce the conductivity slightly, the greatly improved CO₂ stability would suggest there is technological potential for these co-doped samples.     

H2SO4 stability of PBI-blend membranes for SO2 electrolysis

For hydrogen to become a serious contender for replacing fossil fuels, the manufacturing thereof has to be further investigated. One such process, the membrane based Hybrid Sulfur (HyS) process, where hydrogen is produced from the electrolysis of SO₂, has received considerable interest recently. Since H₂SO₄ is formed during SO₂ electrolysis, H₂SO₄ stability is a prerequisite for any membrane to be used in this process. In this study, pure as well as blended polybenzimidazole (PBI), partially fluorinated poly(arylene ether) (sFS) and nonfluorinated poly(arylene ethersulfone) (sPSU) membranes were investigated in terms of their acid stability as a function of acid concentration. Membranes were characterized using weight change, TGA, GPC, SEM/EDX and IEC. While a general stability was observed at 30 and 60 wt% H₂SO₄, the blended sFS-PBI and sPSU-PBI showed the highest stability throughout. According to the VI curve obtained for the SO₂ electrolysis, the sPSU-PBI blend membrane performed slightly better than Nafion^®117.     

SnO2 functionalized AlGaN/GaN high electron mobility transistor for hydrogen sensing applications

In this study, we report on a demonstration of hydrogen sensing at low temperature using SnO₂ functionalized AlGaN/GaN high electron mobility transistors (HEMT). The SnO₂ dispersion was synthesized via a hydrothermal method and selectively deposited on the gate region of a HEMT device through a photolithography process. The high electron sheet carrier concentration of nitride HEMTs provides an increased sensitivity relative to simple Schottky diodes fabricated on GaN layers. The morphology and crystalline properties of the SnO₂-gate, together with the texture of the multilayer films on the device were investigated by SEM, HRTEM, EDS and XRD. The effects of annealing treatment on the crystalline properties of the SnO₂-gate, and gas sensing properties of SnO₂-gated HEMT sensors were studied. The SnO₂-gated HEMT sensor showed fast and reversible hydrogen gas sensing response at low temperature.     

Evaluation of Ni80Cr20/(La0.75Sr0.25)0.95MnO3 dual layer coating on SUS 430 stainless steel used as metallic interconnect for solid oxide fuel cells

Ni₈₀Cr₂₀/(La_0.75Sr_0.25)_0.95MnO₃ dual-layer coating is deposited on SUS 430 alloy by plasma spray for solid oxide fuel cell (SOFC) interconnect application. The phase structure, area specific resistance (ASR), and morphology of the coating are studied. A two-cell stack is also assembled and tested to evaluate coating performance in an actual SOFC stack. The NiCr/LSM coating adheres well to the SUS 430 alloy after oxidation in air at 800 °C for 2800 h. The ASR and its increasing rate of coated alloy are 25 mΩ cm² and 0.0017 mΩ cm²/h, respectively. In an actual stack test, the maximum output power density of the stack repeating unit increases from 0.32 W cm⁻² to 0.45 W cm⁻² because of the application of NiCr/LSM coating. The degradation rate of the stack repeating unit with no coating is 4.4%/100 h at a current density of 0.36 A cm⁻², whereas the stack repeating unit with NiCr/LSM coating exhibits no degradation. Ni₈₀Cr₂₀/(La_0.75Sr_0.25)_0.95MnO₃ dual-layer coating can remarkably improve the thermal stability and electrical performance of metallic interconnects for SOFCs.     

Life cycle assessment of H2 generation with high temperature electrolysis

Water electrolysis is a well-established process for hydrogen production but requires efficiency improvements to reduce costs. High temperature electrolysis (HTE) as a means to higher efficiency was advanced in the EU project RelHY. Through Life Cycle Assessment (LCA), also the environmental performance of five HTE-based hydrogen production systems was evaluated: operation with power and steam from a nuclear plant, continuous and intermittent operation with wind power and water, intermittent operation with natural gas or biogas reforming as back-up. Large scale natural gas reforming (NGR) was used as a reference. The LCA aims to identifying environmental hotspots of HTE plants and comparing their operation. The results show that stack manufacturing has the strongest impact during construction of the HTE plant while the impacts during H₂ production are largely due to power supply. All HTE variants studied lead to less life cycle CO₂-equivalent emissions than NGR. However, only the wind powered HTE variants without back-up use less energy than NGR. The other impacts and flows show different patterns. The results and limitations of the study are discussed.