Chemical and isotopic composition of geothermal discharges from the Puyehue-Cordón Caulle area (40.5°S), Southern Chile

The Puyehue-Cordón Caulle area (40.5°S) hosts one of the largest active geothermal systems of Southern Chile, comprising two main thermal foci, Cordón Caulle and Puyehue. Cordón Caulle is a NW-trending volcanic depression dominated by fumaroles at the top (1500 m) and boiling springs at the northwest end (1000 m). In the latter, the alkaline-bicarbonate composition of the springs with low Mg (<0.06 mg/l) relative to the local meteoric waters (5 mg/l), low chloride (<60 mg/l), high silica (up to 400 mg/l) and δ¹⁸O–δD values close to the Global Meteoric Water Line (GMWL), in combination with the large outflow (100 l/s), suggest the existence of a secondary steam-heated aquifer overlying a main vapor-dominated system at Cordón Caulle. Subsurface temperatures of the secondary aquifer are estimated to be about 170–180 °C (corrected silica geothermometers). The Puyehue thermal area, on the other hand, includes Mg-rich hot springs discharging along stream valleys, with maximum temperatures of 65 °C and a δ¹⁸O–δD signature resembling the local meteoric composition, which suggests that the surface manifestations contain a reservoir component that is strongly diluted by meteoric waters. Topographic/hydrologic and chemical characteristics suggest that Cordón Caulle and Puyehue represent two separate upflows.     

Gas chemistry and helium isotopes at Cerro Prieto

Seven producing wells and seven hot springs in the Cerro Prieto geothermal field were sampled during April and September 1977, for determination of gas chemistry and helium isotope ratios. Well gases are remarkably uniform in gas chemistry and helium isotope ratio, showing high ³He/⁴He ratios characteristic of mantle-derived helium, and higher than expected N₂/Ar ratios. Comparison with the hot spring data suggests that the deep gas component observed in wells is modified during transit to the hot springs by addition of crustal helium, dissolved air and possibly organic methane; alternatively, chemical re-equilibration at lower temperatures may be responsible for increasing the CH₄/H₂ ratio.     

Hydrology,hydrochemistry and geothermal potential of El Chichón volcano-hydrothermal system,Mexico

Fluid and heat discharge rates of thermal springs of El Chichón volcano were measured using the chloride inventory method. Four of the five known groups of hot springs discharge near-neutral Na–Ca–Cl–SO₄ waters with a similar composition (Cl ∼ 1500–2000 mg kg⁻¹ and Cl/SO₄ ∼ 3) and temperatures in the 50–74 °C range. The other group discharges acidic (pH 2.2–2.7) Na–Cl water of high salinity (>15 g/L). All five groups are located on the volcano slopes, 2–3 km in a straight line from the bottom of the volcano crater. They are in the upper parts of canyons where thermal waters mix with surface meteoric waters and form thermal streams. All these streams flow into the Río Magdalena, which is the only drainage of all thermal waters coming from the volcano. The total Cl and SO₄ discharges measured in the Río Magdalena downstream from its junction with all the thermal streams are very close to the sum of the transported Cl and SO₄ by each of these streams, indicating that the infiltration through the river bed is low. The net discharge rate of hydrothermal Cl measured for all thermal springs is about 468 g s⁻¹, which corresponds to 234 kg s⁻¹ of hot water with Cl = 2000 mg kg⁻¹. Together with earlier calculations of the hydrothermal steam output from the volcano crater, the total natural heat output from El Chichón is estimated to be about 160 MWt. Such a high and concentrated discharge of thermal waters from a hydrothermal system is not common and may indicate the high geothermal potential of the system. For the deep water temperatures in the 200–250 °C range (based on geothermometry), and a mass flow rate of 234 kg s⁻¹, the total heat being discharged by the upflowing hot waters may be 175–210 MWt.     

Synthesis and performance of lithium vanadium phosphate as cathode materials for lithium ion batteries by a sol–gel method

Monoclinic lithium vanadium phosphate, Li₃V₂(PO₄)₃, was synthesized by a sol–gel method under Ar/H₂ (8% H₂) atmosphere. The influence of sintering temperatures on the synthesis of Li₃V₂(PO₄)₃ has been investigated using X-ray diffraction (XRD), SEM and electrochemical methods. XRD patterns show that the Li₃V₂(PO₄)₃ crystallinity with monoclinic structure increases with the sintering temperature from 700 to 800 °C and then decreases from 800 to 900 °C. SEM results indicate that the particle size of as-prepared samples increases with the sintering temperature increase and there is minor carbon particles on the surface of the sample particles, which are very useful to enhance the conductivity of Li₃V₂(PO₄)₃. Charge–discharge tests show the 800 °C-sample exhibits the highest initial discharge capacity of 131.2 mAh g⁻¹ at 10 mA g⁻¹ in the voltage range of 3.0–4.2 V with good capacity retention. CV experiment exhibits that there are three anodic peaks at 3.61, 3.70 and 4.11 V on lithium extraction as well as three cathodic peaks at 3.53, 3.61 and 4.00 V on lithium reinsertion at 0.02 mV s⁻¹ between 3.0 and 4.3 V. It is suggested that the optimal sintering temperature is 800 °C in order to obtain pure monoclinic Li₃V₂(PO₄)₃ with good electrochemical performance by the sol–gel method, and the monoclinic Li₃V₂(PO₄)₃ can be used as candidate cathode materials for lithium ion batteries.     

Synthesis of nano-crystalline Sr2MgMoO6−δ anode material by a sol–gel thermolysis method

Nano-crystalline Sr₂MgMoO_6−δ (SMMO) powders were synthesized successfully by a novel sol–gel thermolysis method using a unique combination of polyvinyl alcohol (PVA) and urea. The decomposition behavior of gel precursor was studied by thermogravimetric-differential thermal analysis (TG/DTA) and the results showed that the double-perovskite phase of SMMO began to form at 1000 °C. The microstructure of the samples had been investigated by X-ray diffraction (XRD), transmission electron microscope (TEM), selected area electron diffraction (SAED), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). XRD patterns confirmed that well-crystalline double-perovskite SMMO powders were obtained by calcining at 1450 °C for 12 h. TEM morphological analysis showed that SMMO powders had a mean particle size around 50–100 nm. The SAED pattern and Raman spectroscopy showed that the SMMO powders were nano-polycrystalline well-developed A(B′_0.5B″_0.5)O₃ type perovskite material. The XPS results demonstrated that the Mo ions in SMMO had been reduced after exposure to H₂. The electric property was studied by four-probe method. The results showed that conductivity was 8.64 S cm⁻¹ in 5.0% H₂/Ar at 800 °C and the activation energies at low temperatures (400–640 °C) and high temperatures (640–800 °C) are about 21.43 and 6.59 kJ mol⁻¹, respectively.     

ZrO2–SiO2/Nafion composite membrane for polymer electrolyte membrane fuel cells operation at high temperature and low humidity

Recast Nafion^® composite membranes containing ZrO₂–SiO₂ binary oxides with different Zr/Si ratios are investigated for polymer electrolyte membrane fuel cells (PEMFCs) at temperatures above 100 °C. Fine particles of the ZrO₂–SiO₂ binary oxides, same as an inorganic filter, are synthesized from a sodium silicate and a carbonate complex of zirconium by a sol–gel technique. The composite membranes are prepared by blending a 10% (w/w) Nafion^®-water dispersion with the inorganic compound. All composite membranes show higher water uptake than unmodified membranes, and the proton conductivity increases with increasing zirconia content at 80 °C. By contrast, the proton conductivity decreases with zirconia content for the composite membranes containing binary oxides at 120 °C. The composite membranes are tested in a 9-cm² commercial single cell at both 80 °C and 120 °C in humidified H₂/air under different relative humidity (RH) conditions. Composite membrane containing the ZrO₂–SiO₂ binary oxide (Zr/Si = 0.5) give the best performance of 610 mW cm⁻¹ under conditions of 0.6 V, 120 °C, 50% RH and 2 atm.     

Performance and stability of composite nickel and molybdenum sulfide-based anodes for SOFC utilizing H2S

Performances of four anode compositions with different weight ratios of Ni_3±xS₂ to MoS₂ (2:1, 1:1, 1:2 and 1:4) were compared for H₂S oxidation in SOFC at 700–850 °C. Their thermal and chemical stability were determined using DSC/TGA, XRD, SEM and NAA. Electrochemical stability was investigated in fuel cell mode under OCV and constant overpotential conditions. It was shown that MoS₂ disappearance previously attributed to its volatility at temperature above 450 °C was instead related to its preliminary oxidation to MoO₃ in fuel cell mode as MoO₃ is highly volatile at temperatures above 600 °C. Suppression of volatility of MoO₃ by addition of Ni_3±xS₂ was shown by DSC/TGA analysis. Highest power density ca. 300 mW cm² at 850 °C was achieved with 1:1 weight ratio anode composition. All four compositions had unstable electrochemical performance which was more pronounced under polarization conditions than at OCV.     

Solid state synthesis of hydrous ruthenium oxide for supercapacitors

A novel solid state route has been successfully developed for the synthesis of nano-scale hydrous ruthenium oxide (denoted as RuO₂·xH₂O). The procedure involves directly mixing RuCl₂·xH₂O with alkali to form RuO₂·xH₂O in a mortar at room temperature. Transmission electron microscopy (TEM) and N₂ adsorption–desorption measurement indicate that the RuO₂·xH₂O particle is approximately 30–40 nm with mesoporous structure. The crystalline structure and the electrochemical properties of RuO₂·xH₂O have been systematically explored as a function of annealing temperature. At lower temperatures, the RuO₂·xH₂O powder was found in an amorphous phase and the maximum capacitance of 655 F g⁻¹ was obtained by annealing at 150 °C. Higher temperatures (exceeding 175 °C) presumably converted amorphous phase into crystalline one and the corresponding specific capacitance dropped rapidly from 547 F g⁻¹ at 175 °C to 87 F g⁻¹ at 400 °C. Also, the dependence of electrochemical performance on annealing conditions of RuO₂·xH₂O was investigated by electrical impedance spectroscopy (EIS) study.     

Thermal stability of Vale Inco nanonometric nickel as a catalytic additive for magnesium hydride (MgH2)

The structure stability of nanometric-Ni (n-Ni) produced by Vale Inco Ltd. Canada as a catalytic additive for MgH₂ has been investigated. Each n-Ni filament is composed of nearly spherical interconnected particles having a mean diameter of 42 ± 16 nm. After ball milling of the MgH₂ + 5 wt.%n-Ni mixture for 15 min the n-Ni particles are found to be uniformly embedded within the particles of MgH₂ and at their surfaces. Neither during ball milling of the MgH₂ + 5 wt.%n-Ni mixture nor its first decomposition at temperatures of 300, 325, 350 and 375 ^°C the elemental n-Ni reacts with the elemental Mg to form the Mg₂Ni intermetallic phase (and eventually the Mg₂NiH₄ hydride). The n-Ni additive acts as a strong catalyst accelerating the kinetics of desorption. From the Arrhenius and Johnson–Mehl–Avrami–Kolmogorov theory the activation energy for the first desorption is determined to be ∼94 kJ/mol. After cycling at 300 ^°C the activation energy for desorption is determined to be ∼99 kJ/mol. This is much lower than ∼160 kJ/mol observed for the undoped and ball milled MgH₂. During cycling at 275 and 300 ^°C the n-Ni additive is converted into Mg₂Ni (Mg₂NiH₄). The newly formed Mg₂NiH₄ has a nanosized grain on the order of 20 nm. Its catalytic potency seems to be similar to its n-Ni precursor. The formation of Mg₂Ni (Mg₂NiH₄) may be one of the factors responsible for the systematic decrease of hydrogen capacity observed upon cycling at 275 and 300 ^°C.     

A symmetrical,planar SOFC design for NASA's high specific power density requirements

Solid oxide fuel cell (SOFC) systems for aircraft applications require an order of magnitude increase in specific power density (1.0 kW kg⁻¹) and long life. While significant research is underway to develop anode supported cells which operate at temperatures in the range of 650–800 °C, concerns about Cr-contamination from the metal interconnect may drive the operating temperature down further, to 750 °C and lower. Higher temperatures, 850–1000 °C, are more favorable in order to achieve specific power densities of 1.0 kW kg⁻¹. Since metal interconnects are not practical at these high temperatures and can account for up to 75% of the weight of the stack, NASA is pursuing a design that uses a thin, LaCrO₃-based ceramic interconnect that incorporates gas channels into the electrodes. The bi-electrode supported cell (BSC) uses porous YSZ scaffolds, on either side of a 10–20 μm electrolyte. The porous support regions are fabricated with graded porosity using the freeze-tape casting process which can be tailored for fuel and air flow. Removing gas channels from the interconnect simplifies the stack design and allows the ceramic interconnect to be kept thin, on the order of 50–100 μm. The YSZ electrode scaffolds are infiltrated with active electrode materials following the high-temperature sintering step. The NASA-BSC is symmetrical and CTE matched, providing balanced stresses and favorable mechanical properties for vibration and thermal cycling.     

Revision,calibration, and application of the volume method to evaluate the geothermal potential of some recent volcanic areas of Latium,Italy

The volume method is used to evaluate the productive potential of unexploited and minimally exploited geothermal fields. The distribution of P_CO2 in shallow groundwaters delimits the geothermal fields. This approach is substantiated by the good correspondence between zones of high CO₂ flux, and the areal extension of explored geothermal systems of high enthalpy (Monte Amiata and Latera), medium enthalpy (Torre Alfina) and low enthalpy (Viterbo). Based on the data available for geothermal fields either under exploitation or investigated by long-term production tests, a specific productivity of 40 t h⁻¹ km⁻³ is assumed. The total potential productivity for the recent volcanic areas of Latium is about 28 × 10³ t h⁻¹, with 75% from low-enthalpy geothermal fields, 17% from medium-enthalpy systems, and 8% from high-enthalpy reservoirs. The total extractable thermal power is estimated to be 2220–2920 MW, 49–53% from low-enthalpy geothermal fields, 28–32% from medium-enthalpy systems, and 19–20% from high-enthalpy reservoirs.     

Silver-perovskite composite SOFC cathodes processed via mechanofusion

Atomized silver spheres (≈20–50 μm diameter) were coated with 1 μm thick layers of (La_0.6Sr_0.4)_0.98Co_0.2Fe_0.8O₃ or Sm_0.5Sr_0.5CoO₃ via a mechanofusion dry processing method. The materials were subsequently assessed as solid oxide fuel cell cathodes on anode-supported YSZ electrolytes at 650–750 °C. The materials were subject to significant electrochemical conditioning during initial cell operation, and factors, such as temperature and operating voltage, affecting the conditioning rate are discussed. Post-conditioned power densities (at 0.7 V) were typically 550–650, 400–450 and 300–350 mW cm⁻² at 750, 700 and 650 °C, respectively. Though power degradation rates of ≈7.5 and 4.5% (per 1000 h) were observed at 750 and 700 °C, respectively, no degradation was detected over almost 2000 h of testing at 650 °C.     

Effect of food to microorganism ratio on biohydrogen production from food waste via anaerobic fermentation

The effect of different food to microorganism ratios (F/M) (1–10) on the hydrogen production from the anaerobic batch fermentation of mixed food waste was studied at two temperatures, 35 ± 2 °C and 50 ± 2 °C. Anaerobic sludge taken from anaerobic reactors was used as inoculum. It was found that hydrogen was produced mainly during the first 44 h of fermentation. The F/M between 7 and 10 was found to be appropriate for hydrogen production via thermophilic fermentation with the highest yield of 57 ml-H₂/g VS at an F/M of 7. Under mesophilic conditions, hydrogen was produced at a lower level and in a narrower range of F/Ms, with the highest yield of 39 ml-H₂/g VS at the F/M of 6. A modified Gompertz equation adequately (R² > 0.946) described the cumulative hydrogen production yields. This study provides a novel strategy for controlling the conditions for production of hydrogen from food waste via anaerobic fermentation.     

Fabrication and characterization of micro-tubular cathode-supported SOFC for intermediate temperature operation

We report the fabrication and characterization of a micro-tubular cathode-supported cell consisting of a Ce_0.9Gd_0.1O_1.95 electrolyte with a Ni–cermet anode on a porous La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ/Ce_0.9Gd_0.1O_1.95 (60:40 volume) tube (460 μm wall thickness and 2.26 mm diameter). The cells were fabricated by a cost-effective technique involving extrusion molding and slurry coating through a co-firing process. Densification of the ceria film (thickness < 15 μm) was successful by co-firing the laminated electrolyte with the porous cathode at 1200 °C. NiO–Ce_0.9Gd_0.1O_1.95 (Ni: Ce_0.9Gd_0.1O_1.95 = 50:50 in volume after reduction) was subsequently sintered on the electrolyte at 1100 °C to construct a 10 μm thick, porous and well-adherent anode. The cell having 1.5 cm tube length fed with humidified 30 vol.% H₂–Ar (3% H₂O) yielded the maximum power densities of 0.16, 0.13 and 0.11 W cm⁻², at 600, 550 and 500 °C, respectively. It was found that the cell performance is strongly dominated by the tube length, due to a high substrate resistance from the cathode current collections.     

Solvent-free,PYR1ATFSI ionic liquid-based ternary polymer electrolyte systems: I. Electrochemical characterization

The electrical properties of solvent-free, PEO–LiTFSI solid polymer electrolytes (SPEs), incorporating different N-alkyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide, PYR_1ATFSI, ionic liquids (ILs), are reported. For this purpose, PYR_1ATFSI materials containing side alkyl groups with different chain-length and branching, i.e., n-propyl, sec-propyl, n-butyl, iso-butyl, sec-butyl and n-pentyl, were properly synthesized and homogeneously incorporated into the SPE samples without phase separation. The addition of ILs to PEO–LiTFSI electrolytes results in a large increase of the conductivity and in a decrease of the interfacial resistance with the lithium metal anode. Most of the PEO–LiTFSI–PYR_1ATFSI samples showed similar ionic conductivities (>10⁻⁴ S cm⁻¹ at 20 °C) and stable interfacial resistance values (400 Ω cm² at 40 °C and 3000 Ω cm² at 20 °C) upon several months of storage. Preliminary battery tests have shown that Li/P(EO)₁₀LiTFSI + 0.96 PYR_1ATFSI/LiFePO₄ solid-state cells are capable to deliver a capacity of 125 mAh g⁻¹ and 100 mAh g⁻¹ at 30 °C and 25 °C, respectively.     

Fabrication, electrochemical characterization and thermal cycling of anode supported microtubular solid oxide fuel cells

This work describes the manufacture and electrochemical characterization of anode supported microtubular SOFC's (solid oxide fuel cells). The cells consist of a Ni-YSZ anode tube of 400 μm wall-thickness and 2.4 mm inner diameter, a YSZ electrolyte of 15-20 μm thickness and a LSM-YSZ cathode. The microtubular anode supporting tubes were prepared by cold isostatic pressing. The deposition of thin layers of electrolyte and cathode are made by spray coating and dip coating respectively. The cells were electrochemically characterized with polarization curves and complex impedance measurements using 5% H₂/95% Ar and 100% of H₂, humidified at 3% as reactant gas in the anodic compartment and air in the cathodic one at temperatures between 750 and 900 °C. The complex impedance measurements show an overall resistance from 1 to 0.42 Ω cm² at temperatures between 750 and 900 °C with polarization of 200 mA cm⁻². The I-V measurements show maximum power densities of 0.3-0.7 W cm⁻² in the same temperature interval, using pure H₂ humidified at 3%. Deterioration in the cathode performance for thin cathodes and high sintering temperatures was observed. They were associated to manganese losses. The cell performance did not present considerable degradation at least after 20 fast shut-down and heating thermal cycles.     

(La0.74Bi0.10Sr0.16)MnO3−δ–(Bi2O3)0.7(Er2O3)0.3 composite cathodes for intermediate temperature solid oxide fuel cells

(La_0.74Bi_0.10Sr_0.16)MnO_3−δ (LBSM)–(Bi₂O₃)_0.7(Er₂O₃)_0.3(ESB) composite cathodes were fabricated for intermediate-temperature solid oxide fuel cells with Sc-stabilized zirconia as the electrolyte. The performance of these cathodes was investigated at temperatures below 750 °C by AC impedance spectroscopy and the results indicated that LBSM–ESB had a better performance than traditional composite electrodes such as LSM–GDC and LSM–YSZ. At 750 °C, the lowest interfacial polarization resistance was only 0.11 Ω cm² for the LBSM–ESB cathode, 0.49 Ω cm² for the LSM–GDC cathode, and 1.31 Ω cm² for the LSM–YSZ cathode. The performance of the cathode was improved gradually by increasing the ESB content, and the performance was optimal when the amounts of LBSM and ESB were equal in composite cathodes. This study shows that the sintering temperature of the cathode affected performance, and the optimum sintering temperature for LBSM–ESB was 900 °C.     

Advances in anodic alumina membranes thin film fuel cell: CsH2PO4 pore-filler as proton conductor at room temperature

Anodic alumina membranes (AAM) filled with cesium hydrogen phosphate proton conductor have been tested as inorganic composite electrolyte for hydrogen–oxygen thin film (≤50 μm) fuel cell (TFFC) working at low temperatures (25 °C), low humidity (T_gas = 25 °C) and low Pt loading (1 mg cm⁻²). Single module TFFC delivering a peak power of around 15–27 mW cm⁻², with open circuit voltage (OCV) of about 0.9 V and short circuit current density in the range 80–160 mA cm⁻² have been fabricated. At variance with pure solid acid electrolytes showing reproducibility problems due to the scarce mechanical resistance, the presence of porous alumina support allowed to replicate similar fuel cell performances over numerous AAM/CsH₂PO₄ assemblies. A scale-up process of the electrodic area has been optimized in order to increase the delivered peak power of AAM thin film fuel cell. Morphological, chemical and electrochemical studies on the alumina composite electrolyte have been carried out by means of scanning electron microscopy, X-ray diffractometry, Micro-Raman spectroscopy, DTA/DTG analysis, ac impedance spectroscopy and single fuel cell tests.     

Electrochemical performances in temperature for a C-containing LiFePO4 composite synthesized at high temperature

C-LiFePO₄ composite was synthesized by mechano-chemical activation using iron and lithium phosphates and also cellulose as carbon precursor; this mixture was heated at 800 °C under argon during a short time. Long-range cyclings at different temperatures (RT, 40 and 60 °C) and at C/20 rate between 2 and 4.5 V vs. Li⁺/Li were carried out with this C-LiFePO₄ material as positive electrode material in lithium cells. Whatever the cycling conditions used, rather good electrochemical performances were obtained, with a capacity close to the theoretical one and a good cycle life, especially at RT – up to 100 cycles – and at 40 °C with ∼80% of the initial capacity maintained after 100 cycles. The electrodes recovered after long-range cyclings were characterized by X-ray diffraction; whatever the cycling temperature no significant structural changes (cell parameters, bond lengths, etc.) were shown to occur. Nevertheless, iron was found to be present at the negative electrode – as already observed by Amine et al. – after long-range cycling at 60 °C: other analyses have to be done to identify the origin of this iron (from an impurity or from LiFePO₄ itself) and to quantify this amount vs. that of active C-LiFePO₄ material using larger cells.     

Physical and electrochemical characterization of Bi2O3-doped scandia stabilized zirconia

Electrolytes based on Sc₂O₃–ZrO₂ exhibit the highest ionic conductivity of zirconia based systems, however, stabilization of the electrochemical properties at operational temperatures, 600–1000 °C, are needed before implementation into SOFCs. Trace additions of Bi₂O₃ are a known sintering aid for zirconia systems. Crystal structures, electrical properties and long-term stability of Bi₂O₃-doped 10ScSZ systems were investigated. The addition of more than 1.0 mol% Bi₂O₃ resulted in suppression of the rhombohedral to cubic phase transformation at 600 °C and cubic phase stabilization at room temperature. The ionic conductivity of 10ScSZ was also improved by Bi₂O₃ additions. A maximum conductivity of 0.034 S cm⁻¹ at 700 °C was observed in 2 mol% Bi₂O₃-doped 10ScSZ sintered at 1300 °C. No phase change was observed in 10ScSZ after annealing at 1000 °C. A certain amount of monoclinic phase, and dramatic conductivity decrease, were observed in Bi₂O₃-doped samples sintered below 1200 °C after annealing. However, 10ScSZ and 2 mol% Bi₂O₃-doped 10ScSZ sintered at 1300 °C show no significant conductivity degradation with annealing. Samples with more than 1 mol% Bi₂O₃ and sintered above 1300 °C resulted in good ionic conductivity and stability.