Mechanical strengthening of Sm-doped CeO2 ceramics by 1 mol% cobalt oxide for solid oxide fuel cell application

Combustion processed nano-sized Ce_0.79Sm_0.20Co_0.01O_2−δ (CSCoO) and Ce_0.80Sm_0.20O_2−δ (CSO) were sintered at various temperatures, and mechanical properties and microstructures were characterized. The results demonstrate that besides a lowering of sintering temperature to achieve sufficient densification, the doping of very minor amounts of CoO (1 mol%) to CSO significantly enhanced mechanical properties. The CSCoO sintered at 1100 °C exhibits a biaxial flexural strength of 354 ± 42 MPa which compared with 194 ± 57 MPa for CSO with a similar relative density sintered at 1400 °C. This slight modification in chemical composition also resulted in a slight improvement in micro-hardness.     

High performance composite interconnect La0.7Ca0.3CrO3/20 mol% ReO1.5 doped CeO2 (Re = Sm,Gd, Y) for solid oxide fuel cells

This paper reports and discusses composite interconnect materials that were modified from La_0.7Ca_0.3CrO_3−δ (LCC) by addition of Re doped CeO₂ (Re = Sm, Gd, Y) for improved conductivity at relative low temperatures. It is found that the addition of small amounts of RDC (ReO_1.5 doped CeO₂) into LCC dramatically increased the electrical conductivity. For the best system studied, LCC + 5 wt% SDC (Sm_0.2Ce_0.8O_1.9), LCC + 3 wt% GDC (Gd_0.2Ce_0.8O_1.9) and LCC + 3 wt% YDC (Y_0.2Ce_0.8O_1.9), the electrical conductivities reached 687.8, 124.6 and 104.8 S cm⁻¹ at 800 °C in air, respectively. The electrical conductivities of the specimens, LCC + 3 wt% SDC, LCC + 1 wt% GDC and LCC + 2 wt% YDC in H₂ at 800 °C were 7.1, 3.8 and 5.9 S cm⁻¹, respectively. With the increase of RDC content, the relative density increased, indicating that RDC served as an effective sintering aid in enhancing the sinterability of the powders. The average coefficient of thermal expansion (CTE) at 30–1000 °C in air increased with the increase of the RDC content. The oxygen permeation measurements indicated a negligible oxygen ionic conduction, indicating that the efficiency loss of a solid oxide fuel cell by permeation is negligible for the general cell design using LCC + RDC as interconnect. Therefore, the composite materials La_0.7Ca_0.3CrO₃/20 mol% ReO_1.5 doped CeO₂ are very promising interconnecting ceramics for solid oxide fuel cells (SOFCs).     

Temperature and stress induced changes of the vibrational response of cubic and rhombohedral 10 mol%Sc2O3-1 mol%CeO2-ZrO2 ceramics

The vibration response of cubic and rhombohedral (β) 10 mol%Sc₂O₃-1 mol%CeO₂-ZrO₂ (Sc_0.1Ce_0.01ZrO₂) both at room and high-temperatures is reported. The in situ heating experiments and ex situ indentation experiments were performed to characterize the vibrational behavior of these important materials. A temperature and stress-assisted phase transition from cubic to rhombohedral phase was detected during in situ Raman spectroscopy experiments. While heating and indentation experiments performed separately did not cause the transition of the cubic phase into the rhombohedral structure under the performed experimental conditions and only broadened or strained peaks of the cubic phase could be detected, the heating of the indented (strained) surface leaded to the formation of the rhombohedral Sc_0.1Ce_0.01ZrO₂. Both temperature range and strained zone were estimated by in situ heating and 2D mapping, where a formation of rhombohedral or retention of cubic phase has been promoted.     

Lithium difluoro(oxalato)borate/ethylene carbonate + propylene carbonate + ethyl(methyl) carbonate electrolyte for LiMn2O4 cathode

Lithium difluoro(oxalato)borate (LiODFB) was investigated as a lithium salt for non-aqueous electrolytes for LiMn₂O₄ cathode in lithium-ion batteries. Linear sweep voltammetry (LSV) tests were used to examine the electrochemical stability and the compatibility between the electrolytes and LiMn₂O₄ cathode. Through inductively coupled plasma (ICP) analysis, we compared the amount of Mn²⁺ dissolved from the spinel cathode in 1 mol L⁻¹ LiPF₆/EC + PC + EMC (1:1:3 wt.%) and 1 mol L⁻¹ LiODFB/EC + PC + EMC (1:1:3 wt.%). AC impedance measurements and scanning electron microscopy (SEM) analysis were used to analyze the formation of the surface film on the LiMn₂O₄ cathode. These results demonstrate that ODFB anion can capture the dissolution manganese ions and form a denser and more compact surface film on the cathode surface to prevent the continued Mn²⁺ dissolution, especially at high temperature. It is found that LiODFB, instead of LiPF₆, can improve the capacity retention significantly after 100 cycles at 25 °C and 60 °C, respectively. LiODFB is a very promising lithium salt for LiMn₂O₄ cathode in lithium-ion batteries.     

Synthesis and electrochemical properties of Li1−xFe0.8Ni0.2O2–LixMnO2 (Mn/(Fe + Ni + Mn) = 0.8) material

A new type of Li_1−xFe_0.8Ni_0.2O₂–Li_xMnO₂ (Mn/(Fe + Ni + Mn) = 0.8) material was synthesized at 350 °C in air atmosphere using a solid-state reaction. The material had an XRD pattern that closely resembled that of the original Li_1−xFeO₂–Li_xMnO₂ (Mn/(Fe + Mn) = 0.8) with much reduced impurity peaks. The Li/Li_1−xFe_0.8Ni_0.2O₂–Li_xMnO₂ cell showed a high initial discharge capacity above 192 mAh g⁻¹, which was higher than that of the parent Li/Li_1−xFeO₂–Li_xMnO₂ (186 mAh g⁻¹). We expected that the increase of initial discharge capacity and the change of shape of discharge curve for the Li/Li_1−xFe_0.8Ni_0.2O₂–Li_xMnO₂ cell is the result from the redox reaction from Ni²⁺ to Ni³⁺ during charge/discharge process. This cell exhibited not only a typical voltage plateau in the 2.8 V region, but also an excellent cycle retention rate (96%) up to 45 cycles.     

Ba0.5Sr0.5Co0.8Fe0.2O3 − δ + LaCoO3 composite cathode for Sm0.2Ce0.8O1.9-electrolyte based intermediate-temperature solid-oxide fuel cells

A novel Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3 − δ + LaCoO₃ (BSCF + LC) composite oxide was investigated for the potential application as a cathode for intermediate-temperature solid-oxide fuel cells based on a Sm_0.2Ce_0.8O_1.9 (SDC) electrolyte. The LC oxide was added to BSCF cathode in order to improve its electrical conductivity. X-ray diffraction examination demonstrated that the solid-state reaction between LC and BSCF phases occurred at temperatures above 950 °C and formed the final product with the composition: La_0.316Ba_0.342Sr_0.342Co_0.863Fe_0.137O_3 − δ at 1100 °C. The inter-diffusion between BSCF and LC was identified by the environmental scanning electron microscopy and energy dispersive X-ray examination. The electrical conductivity of the BSCF + LC composite oxide increased with increasing calcination temperature, and reached a maximum value of ∼300 S cm⁻¹ at a calcination temperature of 1050 °C, while the electrical conductivity of the pure BSCF was only ∼40 S cm⁻¹. The improved conductivity resulted in attractive cathode performance. An area-specific resistance as low as 0.21 Ω cm² was achieved at 600 °C for the BSCF (70 vol.%) + LC (30 vol.%) composite cathode calcined at 950 °C for 5 h. Peak power densities as high as ∼700 mW cm⁻² at 650 °C and ∼525 mW cm⁻² at 600 °C were reached for the thin-film fuel cells with the optimized cathode composition and calcination temperatures.     

Structural evolution of ramsdellite-type LixTi2O4 upon electrochemical lithium insertion–deinsertion (0 ≤ x ≤ 2)

Structural evolution during topotactical electrochemical lithium insertion and deinsertion reactions in ramsdellite-like Li_xTi₂O₄ has been followed by means of in situ X-ray diffraction techniques. The starting Li_xTi₂O₄ (x = 1) exists as a single phase with variable composition which extends in the range 0.50 ≤ x ≤ 1.33. However, beyond the lower and upper compositional limits, two other single phases, with ramsdellite-like structure, are detected. The composition of these single phases are: TiO₂ upon lithium deinsertion and Li₂Ti₂O₄ upon lithium insertion. Both TiO₂ and Li₂Ti₂O₄ are characterized by narrow compositional ranges. The close structural relationship between pristine LiTi₂O₄ and the inserted and deinserted compounds together with the relative small volume change over the whole insertion–deinsertion range (not more than 1.1% upon reduction) is a guaranty for the high capacity retention after long cycling in lithium batteries. The small changes in cell parameters well reflect the remarkable flexibility of the ramsdellite framework against lithiation and delithiation reactions.     

Mechanical behavior and electrical conductivity of La1−xCaxCoO3 (x = 0, 0.2, 0.4, 0.55) perovskites

This paper compares the important mechanical properties and the electrical conductivities from room temperature to 800 °C of four LaCoO₃ based cobaltite compositions with 0, 20, 40 and 55% Ca²⁺ ions substituted on the A site of the perovskite structure respectively. Ca²⁺ doped lanthanum cobaltite materials are strong candidates for use as cathodes in lower temperature solid oxide fuel cells operating at or below 800 °C. Among these four cobaltite compositions, two (LaCoO₃ and La_0.8Ca_0.2CoO₃) were found to be phase pure materials, whereas the remaining two compositions (La_0.6Ca_0.4CoO₃ and La_0.45Ca_0.55CoO₃) contained precipitation of secondary phases such as CaO and Co₃O₄. The mechanical properties of the four compositions, in terms of Young's modulus, four-point bending strength and fracture toughness measurements, were measured at both room temperature and 800 °C. At room temperature, doping with Ca²⁺ was found to substantially increase the mechanical properties of the cobaltites, whereas at 800 °C the pure LaCoO₃ composition exhibited higher modulus and strength values than La_0.8Ca_0.2CoO₃. All of the four compositions exhibited ferroelastic behavior, as shown by the hysteresis loops generated during uniaxial load-unload compression tests. Electrical conductivity measurements showed the La_0.8Ca_0.2CoO₃ composition to have the highest conductivity among the four compositions.     

Oxidation of methanol on perovskite-type La2-xSrxNiO4 (0 ≤ x ≤ 1) film electrodes modified by dispersed nickel in 1 M KOH

Finely-dispersed nickel particles are electrodeposited on high surface-area perovskite-type La_2-xSr_xNiO₄ (0 ≤ x ≤ 1) electrodes for possible use in a direct methanol fuel cell (DMFC). The study is conducted by cyclic voltammetry, chronoamperometry, impedance spectroscopy and anodic Tafel polarization techniques. The results show that the apparent electrocatalytic activities of the modified oxide electrodes are much higher than those of unmodified electrodes under similar experimental conditions; the observed activity is the greatest with the modified La_1.5Sr_0.5NiO₄ electrode. At 0.550 V (vs. Hg|HgO) in 1 M KOH + 1 M CH₃OH at 25 °C, the latter electrode delivers a current density of over 200 mA cm⁻², whereas other electrodes of the series produce relatively low values (65–117 mA cm⁻²). To our knowledge, such high methanol oxidation current densities have not been reported on any other non-platinum electrode in alkaline solution. Further, the modified electrodes are not poisoned by methanol oxidation intermediates/products.     

The influence of compositional change of 0.3Li2MnO3·0.7LiMn1−xNiyCo0.1O2 (0.2 ≤ x ≤ 0.5, y = x − 0.1) cathode materials prepared by co-precipitation

Cathode materials prepared by a co-precipitation are 0.3Li₂MnO₃·0.7LiMn_1−xNi_yCo_0.1O₂ (0.2 ≤ x ≤ 0.4) cathode materials with a layered-spinel structure. In the voltage range of 2.0-4.6 V, the cathodes show more than one redox reaction peak during its cyclic voltammogram. The Li/0.3Li₂MnO₃·0.7LiMn_1−xNi_yCo_0.1O₂ (x = 0.3, y = 0.2) cell shows the initial discharge capacity of about 200 mAh g⁻¹. However, when x = 0.2 and y = 0.1, the cell exhibits a rapid decrease in discharge capacity and poor cycle life.     

Structural and electrochemical characterization of xLi[Li1/3Mn2/3]O2·(1 − x)Li[Ni1/3Mn1/3Co1/3]O2 (0 ≤ x ≤ 0.9) as cathode materials for lithium ion batteries

A series of cathode materials with molecular notation of xLi[Li_1/3Mn_2/3]O₂·(1 − x)Li[Ni_1/3Mn_1/3Co_1/3]O₂ (0 ≤ x ≤ 0.9) were synthesized by combination of co-precipitation and solid state calcination method. The prepared materials were characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) techniques, and their electrochemical performances were investigated. The results showed that sample 0.6Li[Li_1/3Mn_2/3]O₂·0.4Li[Ni_1/3Mn_1/3Co_1/3]O₂ (x = 0.6) delivers the highest capacity and shows good capacity-retention, which delivers a capacity ∼250 mAh g⁻¹ between 2.0 and 4.8 V at 18 mA g⁻¹.     

Structural and thermal properties of boron nanoparticles synthesized from B2O3 + 3Mg + kNaCl mixture

Amorphous boron nanoparticles were synthesized by heating a B₂O₃ + 3 Mg + kNaCl (k is the number of moles of NaCl) exothermic mixture in a laboratory oven at 800 °C under argon flow. NaCl was used as inert material to decrease the maximum combustion temperature of the reaction mixture when it was self-ignited after the melting of Mg at 650 °C. The size of the boron nanoparticles extracted from the final product by acid leaching ranged between 30 and 300 nm for k values ranging from 1 to 5. Moreover, increasing the value of k from 1 to 5 resulted in an increase in the specific surface area of the nanoparticles from 40 to 74 m² g⁻¹. However, at k = 10, a decrease in the specific surface area to 47.56 m² g⁻¹ was recorded due to incomplete reduction of B₂O₃. The ignition point of boron nanoparticles in air as estimated using a thermocouple was approximately 300 °C. Digital camera recording of the combustion process of boron nanoparticles in air revealed that the burning speed of the nanoparticles increased significantly from 0.3 to 15 cm/s when k increased from 1 to 5.     

Behavior of 3 mol% yttria-stabilized tetragonal zirconia polycrystal film prepared by slurry spin coating

A dense and uniform 3 mol% yttria-stabilized tetragonal zirconia polycrystal (3YSZ) electrolyte film of 6 μm in thickness was fabricated by slurry spin coating on a porous NiO/3YSZ anode substrate. Composite cathodes of La_0.7Sr_0.3MnO₃ impregnated with Sm_0.2Ce_0.8O_1.9 were fabricated on the 3YSZ films. A single cell produced in this way was tested at 700, 750 and 800 °C with hydrogen as fuel and stationary air as oxidant. Test results revealed an open-circuit voltage of 1.04 V at 800 °C, and maximum power density of 551, 895 and 1143 mW cm⁻² at 700, 750 and 800 °C, respectively. Impedance spectra results demonstrated that the cell performance was determined by the polarization resistance of the cathode.     

Li2MSiO4 (M = Fe and/or Mn) cathode materials

Two iso-structural end members of the family of orthosilicates, i.e. Li₂MSiO₄ (M = Mn and Fe) and their solid solutions, were prepared and electrochemically characterized for potential use in Li-ion batteries. Due to the low specific conductivity (∼5 × 10⁻¹⁶ S cm⁻¹ for Li₂MnSiO₄ and ∼6 × 10⁻¹⁴ S cm⁻¹ for Li₂FeSiO₄ at room temperature), small particles in an intimate contact with a conducting phase (i.e. carbon) are needed. Li₂MSiO₄/C composites (M = Mn and/or Fe) prepared by the Pechini synthesis generally leads to 30–50 nm large particles embedded in a carbon matrix. The amount of carbon in the composite is close to 10 wt.% for the Li₂FeSiO₄/C composite and slightly more than 5 wt.% for the Li₂MnSiO₄/C composite. In situ XRD experiment confirms a structural collapse of Li₂MnSiO₄ and the observed structural stability is completely different for Li₂FeSiO₄, which undergoes a fully reversible two-phase transition. Solid solutions between Li₂MnSiO₄ and Li₂FeSiO₄ in principle lead to higher capacities (>1e⁻ per transition metal is feasible). For a long-term operation the cut-off voltage should be properly chosen. Electrochemical characterisation and in situ XRD experiments suggest the use of cut-off voltage close to 4.2 V.     

Electrochemical behavior of Li3−xM′xV2−yM″y(PO4)3 (M′ = K, M″ = Sc, Mg + Ti)/C composite cathode material for lithium-ion batteries

Composites of monoclinic Li_3−xM′_xV_2−yM″_2y(PO₄)₃ (M′ = K, M″ = Sc, Mg + Ti) with carbon were synthesized by solid-state reaction using oxalic acid or 6% H₂/Ar gas mixture as reducing agents at sintering temperature of 850 °C. The samples were characterized by X-ray diffraction (XRD), voltammetry and electrochemical galvanostatic cycling. The capacity of Li₃V₂(PO₄)₃ synthesized using hydrogen as the reducing agent was 127 mA h g⁻¹ and decreased to 120 mA h g⁻¹ after 20 charge-discharge cycles. The substitution of lithium and vanadium for other ions did not result in the improvement of the electrochemical characteristics of the samples.     

Effect of oxygen non-stoichiometry and temperature on cation ordering in LiMn2−xNixO4 (0.50 ≥ x ≥ 0.36) spinels

The effect of oxygen stoichiometry on the transition metal ordering and electrochemical activity of LiMn_2−xNi_xO₄ solid solutions was investigated. Temperature–oxygen-partial-pressure–composition (pO₂–T–x) diagrams of ordered and disordered phases of LiMn_2−xNi_xO₄ (0.50 ≥ x ≥ 0.36) in the vicinity of order–disorder transition temperature (T_c) was constructed by means of infrared spectroscopy, thermogravimetric analysis and galvanostatic measurements. Despite their simplicity and limitations over traditional diffraction techniques, all three techniques offered near excellent capability to distinguish ordered and disordered phases. The effect of oxygen-partial-pressure (pO₂) in the annealing atmosphere and nickel content of the spinel on T_c was studied. The transition temperature increased with pO₂ and nickel content, except in oxygen-rich (pO₂ = 1) atmosphere for the maximum nickel content spinel of LiMn_1.5Ni_0.5O₄. An explanation for the dependence of the transition temperature on the two variables and changes induced by the post-fabrication heat treatments is provided.     

Influence of multiple oxide (Cr2O3/Nb2O5) addition on the sorption kinetics of MgH2

The influence of multiple additions of two oxides, Cr₂O₃ and Nb₂O₅, as additives on the hydrogen sorption kinetics of MgH₂ after milling was investigated. We found that the desorption kinetics of MgH₂ were improved more by multiple oxide addition than by single addition. Even for the milled MgH₂ micrometric size powders, the high hydrogen capacity with fast kinetics were achieved for the powders after addition of 0.2 mol% Cr₂O₃ + 1 mol% Nb₂O₅. For this composition, the hydride desorbed about 5 wt.% hydrogen within 20 min and absorbed about 6 wt.% in 5 min at 300 °C. Furthermore, the desorption temperature was decreased by 100 °C, compared to MgH₂ without any oxide addition, and the activation energy for the hydrogen desorption was estimated to be about 185 kJ mol⁻¹, while that for MgH₂ without oxide was about 206 kJ mol⁻¹.     

La0.4Ce0.6O1.8–La0.8Sr0.2MnO3–8 mol% yttria-stabilized zirconia composite cathode for anode-supported solid oxide fuel cells

The composite cathodes of La_0.4Ce_0.6O_1.8 (LDC)–La_0.8Sr_0.2MnO₃ (LSM)–8 mol% yttria-stabilized zirconia (YSZ) with different LDC contents were investigated for anode-supported solid oxide fuel cells with thin film YSZ electrolyte. The oxygen temperature-programmed desorption profiles of the LDC–LSM–YSZ composites indicate that the addition of LDC increases surface oxygen vacancies. The cell performance was improved largely after the addition of LDC, and the best cell performance was achieved on the cells with the composite cathodes containing 10 wt% or 15 wt% LDC. The electrode polarization resistance was reduced significantly after the addition of LDC. At 800 °C and 650 °C, the polarization resistances of the cell with a 10 wt% LDC composite cathode are 70% and 40% of those of the cell with a LSM–YSZ composite cathode, respectively. The impedance spectra show that the processes associated with the dissociative adsorption of oxygen and diffusion of oxygen intermediates and/or oxygen ions on LSM surface and transfer of oxygen species at triple phase boundaries are accelerated after the addition of LDC.     

Bulk conduction and relaxation in [(ZrO2)1−x(CeO2)x]0.92(Y2O3)0.08 (0 ≤ x ≤ 1) solid solutions at intermediate temperatures

Bulk conduction and relaxation of the [(ZrO₂)_1−x(CeO₂)_x]_0.92(Y₂O₃)_0.08 (0 ≤ x ≤ 1) solid solutions were studied using impedance spectroscopy at intermediate temperatures (200-500 °C). The bulk conductivity as a function of x shows a “V-shape” variation which is a competitive effect of the defect associates and the lattice parameter. In the ZrO₂-rich region (x < 0.5) CeO₂ doping increases the concentration of defect associates which limits the mobility of the oxygen vacancies; in the CeO₂-rich region (x > 0.5) the increase of x increases the lattice parameter which enlarges the free channel for oxygen vacancy migration. Further analysis indicates the ionic radius of the tetravalent dopant determines the composition dependence of the ionic conductivity of the solid solutions. When doping YSZ with other tetravalent dopant with similar ionic radius with Zr⁴⁺, e.g., Hf⁴⁺, such “V-shape” composition dependence of the bulk conductivity cannot be observed.     

Electrochemical studies of low-temperature processed nano-crystalline LiMn2O4 thin film cathode at 55 °C

LiMn₂O₄ thin films with nano-crystals less than 100 nm were successfully grown on polished stainless steel substrates at 400 °C and 200 m Torr of oxygen by pulsed laser deposition. A maximum discharge capacity of 62.4 μAh cm⁻² μm⁻¹ cycled between 3.0 and 4.5 V with a current density of 20 μAh cm⁻² was achieved. The effect of several overdischarge cycles was negligible, and both the effect of Jahn–Teller distortion at low potentials on capacity loss and structure instability at high potentials were effectively inhibited in this nano-crystalline film, resulting in an excellent cycling stability with a very low fading rate of capacity up to 500 cycles at 55 °C.