RuxCrySez electrocatalyst loading and stability effects on the electrochemical performance in a PEMFC

The present paper presents a study of the Ru_xCr_ySe_z chalcogenide electrocatalyst based on physical–chemical characterization through scanning electron (SEM), atomic force (AFM) microscopy and energy dispersion elemental analysis (EDS), thermal stability using differential scanning calorimeter (DSC), electrochemical kinetics towards the oxygen reduction reaction (ORR) in acid media by rotating ring-disk electrode (RRDE) and single and three-stack membrane-electrode assembly (MEA) performance as a function of catalyst loading (10%, 20% and 40% W from 0.2 to 2 mg cm⁻²). Results indicate an electrocatalyst with chemical composition of Ru₆Cr₄Se₅. AFM images showed 80–160 nm nanoparticle agglomerates. Good thermal stability of the cathode Ru₆Cr₄Se₅ was established after 100 h of continuous operation. The electrochemical kinetics study (RRDE) resulted in a electrocatalyst with high activity towards the ORR, preferentially proceeding via 4e⁻ charge transfer pathway towards water formation (i.e., O₂+4H⁺+4e⁻→2H₂O), with a maximum of 2.8% H₂O₂ formation at 25 °C. Finally, MEA tests revealed a maximum power density of 220 mW cm⁻² with a catalyst loading of 20 wt% at 1.6 mg cm⁻².     

Comparative study of oxygen reduction reaction on RuxMySez (M = Cr, Mo, W) electrocatalysts for polymer exchange membrane fuel cell

Electrochemical evaluation of the Ru_xM_ySe_z (M = Cr, Mo, W) type electrocatalysts towards the oxygen reduction reaction (ORR) is presented. The electrocatalysts were synthesized by reacting the corresponding transition metal carbonyl compounds and elemental selenium in 1,6-hexanediol under refluxing conditions for 3 h. The powder electrocatalysts were characterized by scanning electron microscopy (SEM), and X-ray diffraction (XRD). Results indicate the formation of agglomerates of crystalline particles with nanometric size embedded in an amorphous phase. The particle size decreased according to the following trend: Ru_xCr_ySe_z > Ru_xW_ySe_z > Ru_xMo_ySe_z. Electrochemical studies were performed by rotating disk electrode (RDE) and rotating ring-disk electrode (RRDE) techniques. Kinetic parameters exhibited Tafel slopes of 120 mV dec⁻¹; exchange current density of around 1 × 10⁻⁵ mA cm⁻² and apparent activation energies between 40 and 55 kJ mol⁻¹. A four-electron reduction was found in all three cases. The catalytic activity towards the ORR decreases according to the following trend: Ru_xMo_ySe_z > Ru_xW_ySe_z > Ru_xCr_ySe_z. However this trend was not maintained when the materials were tested as cathode electrodes in a single polymer exchange membrane fuel cell, PEMFC. The Ru_xW_ySe_z electrocatalyst showed poor activity compared to Ru_xMo_ySe_z and Ru_xCr_ySe_z which were considered suitable candidates to be used as cathode in PEMFCs.     

Methoxy methane (dimethyl ether) as an alternative fuel for direct fuel cells

The electrooxidation of methoxy methane (dimethyl ether) was studied at different Pt-based electrocatalysts in a standard three-electrode electrochemical cell. It was shown that alloying platinum with ruthenium or tin leads to shift the onset of the oxidation wave towards lower potentials. On the other hand, the maximum current density achieved was lower with a bimetallic catalyst compared to that obtained with a Pt catalyst. The direct oxidation of dimethoxy methane in a fuel cell was carried out with Pt/C, PtRu/C and PtSn/C catalysts. When Pt/C catalyst is used in the anode, it was shown that the pressure of the fuel and the temperature of the cell played important roles to enhance the fuel cell electrical performance. An increase of the pressure from 1 to 3 bar leads to multiply by two times the maximum achieved power density. An increase of the temperature from 90 to 110 °C has the same effect. When PtRu/C catalyst is used in the anode, it was shown that the electrical performance of the cell was only a little bit enhanced. The maximum power density only increased from 50 to 60 mW cm⁻² at 110 °C using a Pt/C anode and a Pt_0.8Ru_0.2/C anode, respectively. But, the maximum power density is achieved at lower current densities, i.e. higher cell voltages. The addition of ruthenium to platinum has other effect: it introduces a large potential drop at relatively low current densities. With the Pt_0.5Ru_0.5/C anode, it has not been possible to applied current densities higher than 20 mA cm⁻² under fuel cell operating conditions, whereas 250 and almost 400 mA cm⁻² were achieved with Pt_0.8Ru_0.2/C and Pt/C anodes. The Pt_0.9Sn_0.1/C anode leads to higher power densities at low current densities and to the same maximum power density as the Pt/C anode.     

Fabrication and testing of a H2–O2 fuel cell using MoxRuySez

We report the results obtained in the preparation and characterization of Mo_xRu_ySe_z electrocatalysts for oxygen reduction reaction and the design, construction and characterization of a H₂–O₂ fuel cell using Mo_xRu_ySe_z. The catalysts were characterized with respect to their electrocatalytic properties. The fuel cell was designed and built with Mo_xRu_ySe_z supported on carbon as cathode, Pt supported on carbon as anode, and H₂SO₄ as the electrolyte. The fuel cell was tested at room temperature and atmospheric pressure. The H₂–O₂ cell showed an efficiency in the order of 30%.     

Chemical and structural instabilities of lithium ion battery cathodes

The chemical and structural stabilities of various layered Li_1−xNi_1−y−zMn_yCo_zO₂ cathodes are compared by characterizing the samples obtained by chemically extracting lithium from the parent Li_1−xNi_1−y−zMn_yCo_zO₂ with NO₂BF₄ in an acetonitrile medium. The nickel- and manganese-rich compositions such as Li_1−xNi_1/3Mn_1/3Co_1/3O₂ and Li_1−xNi_0.5Mn_0.5O₂ exhibit better chemical stability than the LiCoO₂ cathode. While the chemically delithiated Li_1−xCoO₂ tends to form a P3 type phase for (1 − x) < 0.5, Li_1−xNi_0.5Mn_0.5O₂ maintains the original O3 type phase for the entire 0 ≤ (1 − x) ≤ 1 and Li_1−xNi_1/3Mn_1/3Co_1/3O₂ forms an O1 type phase for (1 − x) < 0.23. The variations in the type of phases formed are explained on the basis of the differences in the chemical lithium extraction rate caused by the differences in the degree of cation disorder and electrostatic repulsions. Additionally, the observed rate capability of the Li_1−xNi_1−y−zMn_yCo_zO₂ cathodes bears a clear relationship to cation disorder and lithium extraction rate.     

Effect of (Al,Mg) substitution in LiNiO2 electrode for lithium batteries

Stabilized lithium nickelate is receiving increased attention as a low-cost alternative to the LiCoO₂ cathode now used in rechargeable lithium batteries. Layered LiNi_1−x−yM_xM_yO₂ samples (M_x = Al³⁺ and M_y = Mg²⁺, where x = 0.05, 0.10 and y = 0.02, 0.05) are prepared by the refluxing method using acetic acid at 750 °C under an oxygen stream, and are subsequently subjected to powder X-ray diffraction analysis and coin-cell tests. The co-doped LiNi_1−x−yAl_xMg_yO₂ samples show good structural stability and electrochemical performance. The LiNiAl_0.05Mg_0.05O₂, cathode material exhibits a reversible capacity of 180 mA h g⁻¹ after extended cycling. These results suggest that the threshold concentration for aluminum and magnesium substitution is of the order of 5%. The co-substitution of magnesium and aluminium into lithium nickelate is considered to yield a promising cathode material.     

Preparation and characterization of composite electrodes of coconut-shell-based activated carbon and hydrous ruthenium oxide for supercapacitors

The relationship between the structure-specific capacitance (F g⁻¹) of a composite electrode consisting of activated coconut-shell carbon and hydrous ruthenium oxide (RuO_x(OH)_y) has been evaluated by impregnating various amounts of RuO_x(OH)_y into activated carbon that is specially prepared with optimum pore-size distribution. The composite electrode shows an enhanced specific capacitance of 250 F g⁻¹ in 1 M H₂SO₄ with 9 wt.% ruthenium incorporated. Chemical and structural characterization of the composites reveals a homogeneous distribution of amorphous RuO_x(OH)_y throughout the porous network of the activated carbon. Electrochemical characterization indicates an almost linear dependence of capacitance on the amount of ruthenium owing to its pseudocapacitive nature.     

Metal oxyfluorides TiOF2 and NbO2F as anodes for Li-ion batteries

Lithium insertion and extraction in to/from the oxyfluorides TiOF₂ and NbO₂F is investigated by galvanostatic cycling, cyclic voltammetry and impedance spectroscopy in cells using Li-metal as a counter electrode at ambient temperature. The host compounds are prepared by low-temperature reaction and characterized by powder X-ray diffraction (XRD), Rietveld refinement and Brunauer, Emmett and Teller (BET) surface area. Crystal structure destruction occurs during the first-discharge reaction with Li at voltages below 0.8–0.9 V for Li_xTiOF₂ as shown by ex situ XRD and at ≤1.4 V for Li_xNbO₂F to form amorphous composites, ‘Li_xTi/NbO_y–LiF’. Galvanostatic discharge–charge cycling of ‘Li_xTiO_y’ in the range 0.005–3.0 V at a current density of 65 mA g⁻¹ gives a capacity of 400 (±5) mAh g⁻¹ during 5–100 cycles with no noticeable capacity fading. This value corresponds to 1.52 mol of recycleable Li/Ti. The coulombic efficiency (η) is >98%. Results on ‘Li_xNbO_y’ show good reversibility of the electrode and a η >98% is achieved only after 10 cycles (range 0.005–3.0 V and at 30 mA g⁻¹) and a capacity of 180 (±5) mAh g⁻¹ (0.97 mol of Li/Nb) was stable up to 40 cycles. In both ‘Li_xTiO_y’ and ‘Li_xNbO_y’, the average discharge and charge voltages are 1.2–1.4 and 1.7–1.8 V, respectively. The impedance spectral data measured during the first cycle and after selected numbers of cycles are fitted to an equivalent circuit and the roles played by the relevant parameters as a function of cycle number are discussed.     

The influence of carbon support porosity on the activity of PtRu/Sibunit anode catalysts for methanol oxidation

In this paper we analyse the promises of homemade carbon materials of Sibunit family prepared through pyrolysis of natural gases on carbon black surfaces as supports for the anode catalysts of direct methanol fuel cells. Specific surface area (S_BET) of the support is varied in the wide range from 6 to 415 m² g⁻¹ and the implications on the electrocatalytic activity are scrutinized. Sibunit supported PtRu (1:1) catalysts are prepared via chemical route and the preparation conditions are adjusted in such a way that the particle size is constant within ±1 nm in order to separate the influence of support on the (i) catalyst preparation and (ii) fuel cell performance. Comparison of the metal surface area measured by gas phase CO chemisorption and electrochemical CO stripping indicates close to 100% utilisation of nanoparticle surfaces for catalysts supported on low (22–72 m² g⁻¹) surface area Sibunit carbons. Mass activity and specific activity of PtRu anode catalysts change dramatically with S_BET of the support, increasing with the decrease of the latter. 10%PtRu catalyst supported on Sibunit with specific surface area of 72 m² g⁻¹ shows mass specific activity exceeding that of commercial 20%PtRu/Vulcan XC-72 by nearly a factor of 3.     

Kinetic study of thermophilic anaerobic digestion of solid wastes from potato processing

Anaerobic treatment of solid wastes from potato processing was studied in completely stirred tank reactors (CSTR) at 55 °C. Special attention was paid to the effect of increased organic loading rate (OLR) on the biogas yield in long-term experiments. Both biogas yield and CH₄ in the biogas decreased with the increase in OLR. For OLR in the range of 0.8 gl⁻¹ d⁻¹–3.4 gl⁻¹ d⁻¹, biogas yield and CH₄ obtained were 0.85 l g⁻¹–0.65 l g⁻¹ and 58%–50%, respectively. Biogas yield y as a function of maximum biogas yield y_m, reaction rate constant k and HRT are described on the basis of a mass balance in a CSTR and a first order kinetic. The value of y_m can be obtained from curve fitting or a simple batch test and k results from plotting y/(y_m−y) against 1/OLR from long-term experiments. In the present study values for y_m and k were obtained as 0.88 l g⁻¹ and 0.089 d⁻¹, respectively. The simple model equations can apply for dimensioning completely stirred tank reactors (CSTR) digesting organic wastes from food processing industries, animal waste slurries or biogas crops.     

Advanced materials for the 3D microbattery

Out recent achievements in the development of three-dimensional (3D) thin film microbatteries on silicon and on microchannel plates (MCP) are presented. In such 3D microbatteries, the battery sandwich-like structure, including electrodes, electrolyte and current collectors, is deposited conformally on all available surfaces, thereby utilizing the dead volume of the substrate. Thin-film molybdenum oxysulfide and iron sulfide cathodes were deposited galvanostatically. XRD, XPS and TOF–SIMS characterizations indicated that the submicron thick MoO_yS_z films were amorphous, with the stoichiometry of the films varying with depth. Electrodeposited FeS_x films have an amorphous, network-like porous structure with nanosize particles. A special flow cell for conformal coating of the perforated substrates was designed. A Li/hybrid polymer electrolyte (HPE)/MoO_yS_z-on-Si 3D half cell ran at i_d = i_ch = 10 μA cm⁻² and room temperature for 100 charge/discharge cycles with 0.1%/cycle capacity loss and 100% Faradaic efficiency. A 3D half cell on MCP exhibited 20 times higher capacity than that of a planar half cell with the same footprint.     

Ni1−xCux alloy-based anodes for low-temperature solid oxide fuel cells with biomass-produced gas as fuel

Ni–Cu alloy-based anodes, Ni_1−xCu_x (x = 0, 0.05, 0.2, 0.3)–Ce_0.8Sm_0.2O_1.9 (SDC), were developed for direct utilization of biomass-produced gas in low-temperature solid oxide fuel cells (LT-SOFCs) with thin film Ce_0.9Gd_0.1O_1.95 electrolytes. The alloys were formed by in situ reduction of Ni_1−xCu_xO_y composites synthesized using a glycine-nitrate technique. The electrolyte films were fabricated with a co-pressing and co-firing technique. Electrochemical performance of the Ni_1−xCu_x–SDC anode supported cells was investigated at 600 °C when humidified (3% H₂O) biomass-produced gas (BPG) was used as the fuel and stationary air as the oxidant. With Ni–Cu alloys as anodes, carbon deposition was substantially suppressed and electrochemical performance of the cells was sustained for much longer periods of time. For example, the power export of a Ni–SDC supported cell was only 50% of the initial value (200 mW cm⁻² at 0.5 V) after 20 min, while Ni_0.8Cu_0.2–SDC supported cells could maintain 90% of the initial power density (250 mW cm⁻² at 0.5 V) over a period of 10 h. The improved performance of the Ni–Cu alloy-based anodes is worth considering in developing SOFCs fueled directly with dilute hydrocarbons such as gases derived from biomass.     

Synthesis and electrochemical properties of Mo-doped Li[Ni1/3Mn1/3Co1/3]O2 cathode materials for Li-ion battery

The layered Li[Ni_(1−x)/3Mn_(1−x)/3Co_(1−x)/3Mo_x]O₂ cathode materials (x = 0, 0.005, 0.01, and 0.02) were prepared by a solid-state pyrolysis method (700, 800, 850, and 900 °C). Its structure and electrochemical properties were characterized by XRD, SEM, XPS, cyclic voltammetry, and charge/discharge tests. It can be learned that the doped sample of x = 0.01 calcined at 800 °C shows the highest first discharge capacity of 221.6 mAh g⁻¹ at a current density of 20 mA g⁻¹ in the voltage range of 2.3–4.6 V, and the Mo-doped samples exhibit higher discharge capacity and better cycle-ability than the undoped one at room temperature.     

Oxygen reduction at carbon supported ruthenium–selenium catalysts: Selenium as promoter and stabilizer of catalytic activity

Carbon supported ruthenium-based catalysts (Ru/C) for the oxygen reduction in acid electrolytes were investigated. A treatment of Ru/C catalysts with selenious acid had a beneficial effect on catalytic activity but no influence on intrinsic kinetic properties, like Tafel slope and hydrogen peroxide generation. Reasons for the increased activity of RuSe_x/C catalysts are discussed. Potential step measurements suggest that at potentials around 0.8 V (NHE) a selenium or selenium-oxygen species protects the catalyst from formation of inactive RuO₂-films. This protective effect leads to an enhanced activity of RuSe_x/C compared to Ru/C. No evidence was found for a catalytically active stoichiometric selenium compound. The active phase may be described as a ruthenium suboxide RuO_x (x < 2) layer integrated in a RuSe_y phase or RuSe_yO_v (y < 2, v < 2) layer at the particle surface.     

High performance rare earth oxides LnOx (Ln = Sc,Y, La,Ce, Pr and Nd) modified Pt/C electrocatalysts for methanol electrooxidation

In this paper, the LnO_x (Ln = Sc, Y, La, Ce, Pr and Nd) modified Pt/C catalysts were prepared by wet precipitation and reduction method. The catalysts were characterized by transmission electron microscopy (TEM), energy dispersive X-ray analysis (EDX) and X-ray diffraction (XRD). TEM showed that the Pt-PrO_x nanoparticles were uniformly dispersed on carbon with an average particle size of 5.0 nm in the Pt₃-(PrO_x)₁/C catalyst. EDX showed that Pt and Pr were successfully loaded on the carbon support without obvious loss. XRD showed that all the Pt/C and LnO_x modified Pt/C electrocatalysts (except for the Pt₃-(ScO_x)₁/C electrocatalyst) displayed the typical character of Pt face centered cubic (fcc) phase, whereas the Pt₃-(ScO_x)₁/C electrocatalyst contained the diffraction pattern of Pt face centered cubic and Sc₂O₃ phase. LnO_x modified Pt/C electrocatalysts were compared with Pt/C in terms of the electrochemical activity and stability for methanol electrooxidation using cyclic voltammetry (CV) and chronoamperometry (CA) in 0.5 M H₂SO₄ + 0.5 M CH₃OH solutions. The results showed that all the LnO_x (except for NdO_x) modified the Pt/C electrocatalysts gave higher catalytic activity and stability than Pt/C. In particular, the Pt₃-(PrO_x)₁/C eloctrocatalyst was found to be superior than others. Under this respect, several Pt-PrO_x/C catalysts with different atomic ratio of Pt/Pr were also identically prepared and characterized. It was found by CV and CA that the Pt₃-(PrO_x)₁/C and Pt₁-(PrO_x)₁/C catalysts showed better catalytic activity and stability than the Pt₅-(PrO_x)₁/C, Pt₁-(PrO_x)₃/C and Pt/C catalysts. The Pt₃-(PrO_x)₁/C and Pt₁-(PrO_x)₁/C catalysts had high catalytic activity and good stability, which could be used as novel electrocatalysts for direct methanol fuel cell.     

Effect of the Sm content on the structure and electrochemical properties of La1.3 − xSmxCaMg0.7Ni9 (x = 0–0.3) hydrogen storage alloys

La_1.3 − xSm_xCaMg_0.7Ni₉ (x = 0–0.3) hydrogen storage alloys were prepared by inductive melting and the effect of the Sm content on the structure and electrochemical properties was investigated in the paper. The Sm substitution for La in La_1.3 − xSm_xCaMg_0.7Ni₉ (x = 0–0.3) alloys does not change the main phase structure (the rhombohedral PuNi₃-type structure), but leads to a shrinkage of unit cell and a decrease of hydrogen storage capacity. With the increase of the Sm content in the alloys, the maximum discharge capacity of electrode decreases from 400.2 (x = 0) to 346.6 mAh g⁻¹ (x = 0.3), but the high-rate dischargeability and cycling stability is improved. After 100 cycles, the capacity retention rate increases from 75 (x = 0) to 85% (x = 0.3).     

High voltage stability of nanostructured thin film catalysts for PEM fuel cells

This paper provides a comparative evaluation of electrocatalyst surface area stability in PEM fuel cells under accelerated durability testing. The two basic electrocatalyst types are conventional carbon-supported dispersed Pt catalysts (Pt/C), and nanostructured thin film (NSTF) catalysts. Both types of fuel cell electrocatalysts were exposed to continuous cycling between 0.6 and 1.2 V, at various temperatures between 65 and 95 °C, with H₂/N₂ on the anode and cathode, while periodic measurements of electrochemical surface area were recorded as a function of the number of cycles. The NSTF electrocatalyst surface areas were observed to be significantly more stable than the Pt/C electrocatalysts. A first order rate kinetic model was applied to the normalized surface area changes as a function of number of cycles and temperature, and two parameters extracted, viz. the minimum stable surface area, S_min, and the activation energy, E_a, for surface area loss in this voltage range. S_min was found to be 10% versus 66%, and E_a 23 kJ mole⁻¹ versus 52 kJ mole⁻¹, for Pt/C versus NSTF-Pt, respectively. The loss of surface area in both cases is primarily the result of Pt grain size increases, but the Pt/C XRD grain sizes increase significantly more than the NSTF grain sizes. In addition, substantial peak shifts occur in the Pt/C CVs, which ultimately end up aligning with the NSTF peak positions, which do not change substantially due to the voltage cycling. NSTF catalysts should be more robust against shut down/start-up, operation near OCV and local H₂ starvation effects.     

Synthesis and characterizations of Li[CrxLi(1−x)/3Mn2(1−x)/3]O2 (0.15 ≤ x ≤ 0.3) cathode materials in rechargeable lithium batteries

A series of Li[Cr_xLi_(1−x)/3Mn_2(1−x)/3]O₂ (0.15 ≤ x ≤ 0.3) cathode materials was prepared by citric acid-assisted, sol–gel process. Sub-micron sized particles were obtained and the X-ray diffraction (XRD) results showed that the crystal structure was similar to layered lithium transition metal oxides (R-3m space group). The electrochemical performance of the cathodes was evaluated over the voltage range 2.0–4.9 V at a current density of 7.947 mA g⁻¹. The Li_1.27Cr_0.2Mn_0.53O₂ electrode delivered a high reversible capacity of up to 280 mAh g⁻¹ during cycling. Li[Cr_xLi_(1−x)/3Mn_2(1−x)/3]O₂ yielded a promising cathode material.     

Electrochemical properties of iodine-containing lithium manganese oxide spinel

Iodine-containing, cation-deficient, lithium manganese oxides (ICCD-LMO) are prepared by reaction of MnO₂ with LiI. The MnO₂ is completely transformed into spinel-structured compounds with a nominal composition of Li_1−δMn_2−2δO₄I_x. A sample prepared at 800 °C, viz. Li_0.99Mn_1.98O₄I_0.02, exhibits an initial discharge capacity of 113 mA h g⁻¹ with good cycleability and rate capability in the 4-V region. Iodine-containing, lithium-rich lithium manganese oxides (ICLR-LMO) are also prepared by reaction of LiMn₂O₄ with LiI, which results in a nominal composition of Li_1+xMn_2−xO₄I_x. Li_1.01Mn_1.99O₄I_0.02 shows a discharge capacity of 124 mA h g⁻¹ on the first cycle and 119 mA h g⁻¹ a on the 20th cycle. Both results indicate that a small amount of iodine species helps to maintain cycle performance.     

Nanocrystalline tin oxides and nickel oxide film anodes for Li-ion batteries

Tin oxides and nickel oxide thin film anodes have been fabricated for the first time by vacuum thermal evaporation of metallic tin or nickel, and subsequent thermal oxidation in air or oxygen ambient. X-ray diffraction (XRD) and scanning electron microscopy (SEM) measurements showed that the prepared films are of nanocrystalline structure with the average particle size <100 nm. The electrochemical properties of these film electrodes were examined by galvanostatic cycling measurements and cyclic voltammetry. The composition and electrochemical properties of SnO_x (1<x<2) films strongly depend on the oxidation temperature. The reversible capacities of SnO and SnO₂ films electrodes reached 825 and 760 mAh g⁻¹, respectively, at the current density of 10 μA cm⁻² between 0.10 and 1.30 V. The SnO_x film fabricated at an oxidation temperature of 600 °C exhibited better electrochemical performance than SnO or SnO₂ film electrode. Nanocrystalline NiO thin film prepared at a temperature of 600 °C can deliver a reversible capacity of 680 mAh g⁻¹ at 10 μA cm⁻² in the voltage range 0.01–3.0 V and good cyclability up to 100 cycles.