Sm0.5Sr0.5CoO3 + Sm0.2Ce0.8O1.9 composite cathode for cermet supported thin Sm0.2Ce0.8O1.9 electrolyte SOFC operating below 600 °C

The cathode is a key component in low temperature solid oxide fuel cells. In this study, composite cathode, 75 wt.% Sm_0.5Sr_0.5CoO₃ (SSC) + 25 wt.% Sm_0.2Ce_0.8O_1.9 (SDC), was applied on the cermet supported thin SDC electrolyte cell which was fabricated by tape casting, screen-printing, and co-firing. Single cells with the composite cathodes sintered at different temperatures were tested from 400 to 650 °C. The best cell performance, 0.75 W cm⁻² peak power operating at 600 °C, was obtained from the 1050 °C sintered cathode. The measured thin SDC electrolyte resistance R_s was 0.128 Ω cm² and total electrode polarization R_p(a + c) was only 0.102 Ω cm² at 600 °C.     

Characterization of Ni porous electrode covered by a thin film of LiMg0.05Co0.95O2

A porous electrode of nickel covered by a thin film of lithium cobaltite doped with magnesium (LiMg_0.05Co_0.95O₂) was prepared in order to protect nickel cathode against dissolution into the molten carbonate. A sol impregnation technique was used to deposit gel precursors on the porous surface of the substrate; the covered substrate was submitted to thermal treatments, which produced a lithium cobaltite layer. The cathode was characterized by the following measurements: biaxial bending test, SEM/EDX analysis, which demonstrated the uniformity of the lithium cobaltite layer and the presence of cobalt homogeneously distributed over the nickel particles, electrical conductivity.

To test the cathodic performance of the material under study a cell was assembled and tested in a 10 cm × 10 cm electrodes area plant. The cell performance during the time was studied carrying out polarization curves for many hours (more than 1000 h). To determine the influence of the cathodic gas composition on the electrode performance the atmosphere was changed maintaining alternatively at a constant value the partial pressure of CO₂ and O₂. In such a way the kinetic effect of the single gas was studied. By the technique of IR interruption the internal resistance of the cell was measured.     

Enhancing the elevated temperature performance of Li/LiMn2O4 cells by reducing LiMn2O4 surface area

Lithium-rich spinels were obtained with the same structure but different surface area by two different synthesis routes, namely the “once-annealed” and the “twice-annealed” methods. The elevated temperature performance of Li/Li_1+xMn₂O₄ cell is significantly improved using a spinel cathode with a small surface area: the cell at 50°C lost 5% of the initial capacity over the first 100 cycles based on a spinel cathode with the small surface area of 1.2 m²/g compared to 8% based on a large one of 6.2 m²/g. Also the mechanism responsible for the reaction of LiMn₂O₄ with LiOH to form lithium-rich spinel has been investigated.     

A rechargeable lithium battery employing a porous thin film of Cu3+δMo6S7.9

Porous, thin films of copper molybdenum sulfides (Cu_3+δMo₆S_7.9), that have been prepared by the technique of painting and subsequent reaction with mixed H₂/H₂S gases at 500 °C, have been used as a cathode material for lithium secondary batteries. The test cell comprised: Li/2 M LiClO₄ in PC-THF (4:6)/Cu_3+δMo₆S_7.9 (porous, thin film). The discharge reaction proceeded via the intercalation of lithium ions into the structural interstices of the cathode material.

The first discharge curve of the cell showed that the porous film could incorporate up to 18 lithium ions per formula unit. The capacity of the thin film was four times higher than that previously reported for powder or pressed-pellet electrodes. The theoretical energy density was 675 W h kg⁻¹, i.e., higher than that of TiS₂ (455 W h kg⁻¹) which is one of the best materials for high-energy lithium batteries. From X-ray diffraction studies of the lithium incorporated in the thin film at each discharge step, it is suggested that there are four incorporation reactions of lithium ions into the cathode. Finally, cycling tests have been conducted at room temperature.     

Electrochemical characteristics of an La0.6Sr0.4Co0.2Fe0.8O3–La0.8Sr0.2MnO3 multi-layer composite cathode for intermediate-temperature solid oxide fuel cells

An La_0.6Sr_0.4Co_0.2Fe_0.8O₃–La_0.8Sr_0.2MnO₃ (LSCF–LSM) multi-layer composite cathode for solid oxide fuel cells (SOFCs) was prepared on an yttria-stabilized zirconia (YSZ) electrolyte by the screen-printing technique. Its cathodic polarization curves and electrochemical impedance spectra were measured and the results were compared with those for a conventional LSM/LSM–YSZ cathode. While the LSCF–LSM multi-layer composite cathode exhibited a cathodic overpotential lower than 0.13 V at 750 °C at a current density of 0.4 A cm⁻², the overpotential for the conventional LSM–YSZ cathode was about 0.2 V. The electrochemical impedance spectra revealed a better electrochemical performance of the LSCF–LSM multi-layer composite cathode than that of the conventional LSM/LSM–YSZ cathode; e.g., the polarization resistance value of the multi-layer composite cathode was 0.25 Ω cm² at 800 °C, nearly 40% lower than that of LSM/LSM–YSZ at the same temperature. In addition, an encouraging output power from an YSZ-supported cell using an LSCF–LSM multi-layer composite cathode was obtained.     

New insights in the polarization resistance of anode-supported solid oxide fuel cells with La0.6Sr0.4Co0.2Fe0.8O3 cathodes

In this study, the polarization resistance of anode-supported solid oxide fuel cells (SOFC) with La_0.6Sr_0.4Co_0.2Fe_0.8O₃ (LSCF) cathodes was investigated by I-V sweep and electrochemical impedance spectroscopy under a series of operating voltages and cathode environments (i.e. stagnant air, flowing air, and flowing oxygen) at temperatures from 550 °C to 750 °C. In flowing oxygen, the polarization resistance of the fuel cell decreased considerably with the applied current density. A linear relationship was observed between the ohmic-free over-potential and the logarithm of the current density of the fuel cell at all the measuring temperatures. In stagnant or flowing air, an arc related to the molecular oxygen diffusion through the majority species (molecular nitrogen) present in the pores of the cathode was identified at high temperatures and high current densities. The magnitude of this arc increased linearly with the applied current density due to the decreased oxygen partial pressure at the interface of the cathode and the electrolyte. It is found that the performance of the fuel cell in air is mainly determined by the oxygen diffusion process. Elimination of this process by flowing pure oxygen to the cathode improved the cell performance significantly. At 750 °C, for a fuel cell with a laser-deposited Sm_0.2Ce_0.8O_1.9 (SDC) interlayer, an extraordinarily high power density of 2.6 W cm⁻² at 0.7 V was achieved in flowing oxygen, as a result of reduced ohmic and polarization resistance of the fuel cell, which were 0.06 Ω cm² and 0.03 Ω cm², respectively. The results indicate that microstructural optimization of the LSCF cathode or adoption of a new cell design which can mitigate the oxygen diffusion limitation in the cathode might enhance cell performance significantly.     

Electrochemical behaviour of amorphous V2O5(-P2O5) cathodes for lithium secondary batteries

The electrochemical behaviour of amorphous vanadium oxides (a-V₂O₅ and a-V₂O₅-P₂O₅) cathodes in lithium cells has been investigated. The reversibility of the cathodes is superior to that Of c-V₂O₅ and the cathodes can operate for> 300 cycles. The relationship between cathode composition and cycle performance has been determined, and P₂O₅, as a network-former, has been found not to harm the reversibility of cathodes. The degradation in capacity with cycling of the Li/a-V₂O₅(-P₂O₅) system is due to deterioration of the anode, i.e., an increased polarization on discharge.     

Study of the charging process of a LiCoO2-based Li-ion battery

A three-electrode Li-ion cell with metallic lithium as the reference electrode was designed to study the charging process of Li-ion cells. The cell was connected to three independent testing channels, of which two channels shared the same lithium reference to measure the potentials of anode and cathode, respectively. A graphite/LiCoO₂ cell with a C/A ratio, i.e., the reversible capacity ratio of the cathode to anode, of 0.985 was assembled and cycled using a normal constant-current/constant-voltage (CC/CV) charging procedure, during which the potentials of the anode and cathode were recorded. The results showed that lithium plating occurred under most of the charging conditions, especially at high currents and at low temperatures. Even in the region of CC charging, the potential of the graphite might drop below 0 V versus Li⁺/Li. As a result, lithium plating and re-intercalating of the plated lithium into the graphite coexist, which resulted in a low charging capacity. When the current exceeded a certain level (0.4C in the present case), increasing the current could not shorten the charging time significantly, instead it aggravated lithium plating and prolonged the CV charging time. In addition, we found that lowering the battery temperature significantly aggravated lithium plating. At −20 °C, for example, the CC charging became impossible and lithium plating accompanied the entire charging process. For an improved charging performance, an optimized C/A ratio of 0.85–0.90 is proposed for the graphite/LiCoO₂ Li-ion cell. A high C/A ratio results in lithium plating onto the anode, while a low ratio results in overcharge of the cathode.     

Compatibility of LiCoO2 and LiMn2O4 cathode materials for Li0.55La0.35TiO3 electrolyte to fabricate all-solid-state lithium battery

In order to improve performance of all-solid-state lithium ion battery with honeycomb structure, a compatibility of two commonly used cathode materials, LiCoO₂ and LiMn₂O₄, to Li_0.55La_0.35TiO₃ (LLT) solid electrolyte was studied. LiCoO₂/honeycomb LLT and LiMn₂O₄/honeycomb LLT half cells were fabricated by the impregnation of mixture of the cathode material with its precursor sol into honeycomb holes followed by the calcination. Impurity phases were observed at interface between LiCoO₂ and honeycomb LLT, while no impurity phase was confirmed in the case of LiMn₂O₄. In half cell test, the LiMn₂O₄/honeycomb LLT cell showed about 6 times larger discharge capacity than the LiCoO₂/honeycomb LLT cell, because of high internal resistance of the LiCoO₂/honeycomb LLT cell caused by the impurity phases. It can be said that the formation of low resistance interface at active material/electrolyte is one of the most important key to improve performance of the all-solid-state battery. Using LiMn₂O₄ instead of LiCoO₂, better interface between cathode material and LLT was obtained.     

Electrochemical reduction of silver vanadium phosphorous oxide, Ag2VO2PO4: Silver metal deposition and associated increase in electrical conductivity

This report details the chemical and associated electrical resistance changes of silver vanadium phosphorous oxide (Ag₂VO₂PO₄, SVPO) incurred during electrochemical reduction in a lithium based electrochemical cell over the range of 0-4 electrons per formula unit. Specifically the cathode electrical conductivities and associated cell DC resistance and cell AC impedance values vary with the level of reduction, due the changes of the SVPO cathode. Initially, Ag⁺ is reduced to Ag⁰ (2 electrons per formula unit or 50% of the calculated theoretical value of 4 electrons per formula unit) accompanied by significant decreases in the cathode electrical resistance, consistent with the formation of an electrically conductive silver metal matrix within the SVPO cathode. As Ag⁺ reduction progresses, V⁵⁺ reduction initiates; once the SVPO reduction process progresses to where the reduction of V⁵⁺ to V⁴⁺ is the dominant process, both the cell and the cathode electrical resistances then begin to increase. If the discharge then continues to where the dominant cathode reduction process is the reduction of V⁴⁺ to V³⁺, the cathode and cell electrical resistances then begin to decrease. The complex cathode electrical resistance pattern exhibited during full cell discharge is an important subject of this study.     

A high-efficiency, compound NH3/H2O-H2O/LiBr absorption-refrigeration system

A high-efficiency, compound absorption-refrigeration system is considered, which is composed of two cooperating absorption units using NH₃/H₂O and H₂O/LiBr solutions, respectively. The heat output from the NH₃/H₂O unit is employed to drive the H₂O/LiBr unit. The thermodynamics of the new system are simulated by using a procedure which showed that very high theoretical coefficients of performance may be obtained (up to 230%) compared to the corresponding theoretical values for the usual single absorption units, which do not exceed 100%.     

Preparation of Pr0.35Nd0.35Sr0.3MnO3−δ/YSZ composite cathode powders for tubular solid oxide fuel cells by microwave-induced monomer gelation and gel combustion synthesis process

A microwave-induced monomer gelation and gel combustion synthesis process was successfully developed to synthesize well-dispersed Pr_0.35Nd_0.35Sr_0.3MnO_3−δ (PNSM)/YSZ composite cathode powders for tubular solid oxide fuel cells (SOFCs). The thermo-gravimetric (TG) analysis of as-prepared ash indicated the decomposition process of most of metal nitrates during gel combustion. The X-ray diffraction (XRD) pattern of the powders calcined at 1000 °C showed only pure PNSM and YSZ phase. Transmission electron microscopy (TEM) revealed that the morphology of powders was characterized with the YSZ particles enwrapped by fine PNSM particles so that PNSM/YSZ composite powders were much better-dispersed compared with the powders made simply by mechanical mixing process. The cell made from PNSM/YSZ composite powder showed lower cathode ohmic resistance and polarization resistance, and produced higher power density subsequently.     

Synthesis and electrochemical studies on Al2O3 coated LiNi0.5Co0.44Fe0.06VO4 for lithium ion batteries

LiNi_0.5Co_0.44Fe_0.06VO₄ cathode material has been synthesized by a citric acid:polyethylene glycol polymeric method at 723 K for 5 h in air. The surface of the LiNi_0.5Co_0.44Fe_0.06VO₄ was coated with various wt.% of Al₂O₃ by a wet chemical procedure and heat treated 873 K for 2 h in air. The samples were characterized by XRD, FTIR, SEM, and TEM techniques. XRD patterns expose that the complete crystalline phase occurred at 723 K and there was no indication of new peaks for the coated samples. FTIR spectra show that the complete removal of organic residues and the formation of LiNi_0.5Co_0.44Fe_0.06VO₄. TG/DTGA results reveal that the formation of LiNi_0.5Co_0.44Fe_0.06VO₄ occurred between 480 and 670 K and the complete crystalline occurred at 723 K. SEM micrographs show the various morphological stages of the polymeric intermediates. TEM micrographs of the pristine LiNi_0.5Co_0.44Fe_0.06VO₄ reveal that the particle size ranged from 130 to 150 nm and Al₂O₃ coating on the fine particles was compact and had an average thickness of about 15 nm. The charge–discharge experiments were carried out between 2.8 and 4.9 V (versus Li) at a current rate of 0.15 C. The 1.0 wt.% Al₂O₃ coated sample had the best electrochemical performance, with an initial capacity of 65 mAh g⁻¹ and capacity retention of 60% after 50 cycles. The electrochemical impedance behavior suggests that the failure of pristine cathode performance is associated with an increase in the impedance growth on the surface of the cathode material upon continuous cycling.     

Durable high-performance Sm0.5Sr0.5CoO3–Sm0.2Ce0.8O1.9 core-shell type composite cathodes for low temperature solid oxide fuel cells

Sm_0.5Sr_0.5CoO₃ (SSC)-Sm_0.2Ce_0.8O_1.9 (SDC) core-shell composite cathodes are synthesized via a polymerizable complex method, and the durability of a cell incorporating the cathodes is examined. Nanocrystalline SSC powders have been coated onto the surfaces of SDC cores to enable the formation of a rigid backbone structure, over which the catalyst phase is effectively dispersed. A symmetrical SSC-SDC |SDC| SSC-SDC half-cell exhibits a polarization resistance of 0.098 Ω cm² at 650 °C. The durability and microstructure of the cathode are investigated by electrochemical impedance spectroscopy and thermo-cycle tests at temperatures in the range of 100 °C-650 °C. After 30 cycles, the polarization resistance is found to increase by 9.04 × 10⁻² Ω cm², a 3.56% rise with respect to the initial resistance. Coarsening of the SSC catalyst phase has been prevented with the use of core-shell type powders, as confirmed by a nearly constant low frequency polarization resistance and a microstructural analysis. The performance of a unit cell comprised of the core-shell type cathode exhibits 1.07 W cm⁻² at 600 °C and 0.62 W cm⁻² at 550 °C.     

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.     

High-temperature superconductor, YBa2Cu307-x as all- solid-state lithium cell

The utility of the high-temperature superconductor, YBa₂Cu₃O_7-itx, as the cathode material for an all-solid-state lithium cell has been examined. The capacity of YBa₂Cu₃O₇-x, is 223 mA h g⁻¹ and the discharge efficiency is> 92%. Measurements of a.c. impedance show that the charge-transfer resistance at the interface of the electrolyte/cathode is very low and increases with the depth-of-discharge of the battery. Studies using X-ray photoelectron spectroscopy (XPS) reveal that the cathode becomes doped with Li⁺ ions as the cell discharges.     

Optimization of La0.6Ca0.4Fe0.8Ni0.2O3-Ce0.8Sm0.2O2 composite cathodes for intermediate-temperature solid oxide fuel cells

Sample of nominal composition La_0.6Ca_0.4Fe_0.8Ni_0.2O₃ (LCFN) was prepared by liquid mix method. The structure of the polycrystalline powder was analyzed with X-ray powder diffraction data. This compound shows orthorhombic perovskite structure with a space group Pnma. In order to improve the electrochemical performance, Sm-doped ceria (SDC) powder was added to prepare the LCFN-SDC composite cathodes. Electrochemical characteristics of the composites have been investigated for possible application as cathode material for an intermediate-temperature-operating solid oxide fuel cell (IT-SOFC). The polarization resistance was studied using Sm-doped ceria (SDC). Electrochemical impedance spectroscopy measurements of LCFN-SDC/SDC/LCFN-SDC test cell were carried out. These electrochemical experiments were performed at equilibrium from 850 °C to room temperature, under both zero dc current intensity and air. The best value of area-specific resistance (ASR) was for LCFN cathode doped with 10% of SDC (LCFN-SDC9010), 0.13 Ω cm² at 850 °C. The dc four-probe measurement exhibits a total electrical conductivity over 100 S cm⁻¹ at T ≥ 600 °C for LCFN-SDC9010 composite cathode.     

Solubility and electrochemical studies of LiFeO2–LiCoO2–NiO materials for the MCFC cathode application

The dissolution of the state-of-the-art lithiated NiO is still considered as one of the main obstacles to the commercialisation of the molten carbonate fuel cell (MCFC). Development of alternative cathode materials has been considered as a main strategy for solving this problem. Ternary compositions of LiFeO₂, LiCoO₂ and NiO are expected to decrease the cathode solubility while ensuring a good electrical conductivity and electrochemical activity towards the oxygen reduction.

In this work, new material compositions in the LiFeO₂–LiCoO₂–NiO ternary system were synthesised using Pechini method and investigating their electrical conductivity by the DC four probe method. Then the influence of the cobalt content in the composition was determined in terms of AC impedance analysis and solubility measurements after 200 h of immersion in Li₂CO₃–Na₂CO₃ at 650 °C. The DC electrical conductivity study reveals the ability of improving the electrical conductivity, adequate for MCFC cathode application, by controlling the Co content of the composition. A special attention was given to the evolution of the open circuit potential as a function of time and to the impedance spectroscopy characterization related to microstructure modifications. Taking into account solubility, electrical conductivity, as well as electrochemical performance in the fuel cell, this study reveals the possibility of using LiFeO₂–LiCoO₂–NiO ternary materials for MCFC cathode.     

A screen-printed Ce0.8Sm0.2O1.9 film solid oxide fuel cell with a Ba0.5Sr0.5Co0.8Fe0.2O3−δ cathode

Screen-printing technology was developed to fabricate Ce_0.8Sm_0.2O_1.9 (SDC) electrolyte films onto porous NiO–SDC green anode substrates. After sintering at 1400 °C for 4 h, a gas-tight SDC film with a thickness of 12 μm was obtained. A novel cathode material of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ was subsequently applied onto the sintered SDC electrolyte film also by screen-printing and sintered at 970 °C for 3 h to get a single cell. A fuel cell of Ni–SDC/SDC (12 μm)/Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ provides the maximum power densities of 1280, 1080, 670, 370, 180 and 73 mW cm⁻² at 650, 600, 555, 505, 455 and 405 °C, respectively, using hydrogen as fuel and stationary air as oxidant. When dry methane was used as fuel, the maximum power densities are 876, 568, 346 and 114 mW cm⁻² at 650, 600, 555 and 505 °C, respectively. The present fuel cell shows excellent performance at lowered temperatures.     

Optimization of BaZr0.1Ce0.7Y0.2O3−δ-based proton-conducting solid oxide fuel cells with a cobalt-free proton-blocking La0.7Sr0.3FeO3−δ-Ce0.8Sm0.2O2−δ composite cathode

BaZr_0.1Ce_0.7Y_0.2O_3−δ (BZCY)-based proton-conducting solid oxide fuel cells (H-SOFC) with a cobalt-free proton-blocking La_0.7Sr_0.3FeO_3−δ-Ce_0.8Sm_0.2O_2-δ (LSF-SDC) composite cathode were fabricated and evaluated. The effect of firing temperature of the cathode layer on the chemical compatibility, microstructure of the cathode and cathode-electrolyte interface, as well as electrochemical performance of single cells was investigated in detail. The results indicated that the cell exhibited the most desirable performance when the cathode was fired at 1000 °C; moreover, at the same firing temperature, the power performance had the least temperature dependence. With humidified hydrogen (∼2% H₂O) as the fuel and ambient air as the oxidant, the polarization resistance of the cell with LSF-SDC cathode fired at 1000 °C for 3 h was as low as 0.074 Ω cm² at 650 °C after optimizing microstructures of the anode and anode-electrolyte interface, and correspondingly the maximum power density achieved as high as 542 mW cm⁻², which was the highest power output ever reported for BZCY-based H-SOFC with a cobalt-free cathode at 650 °C.