Interlayer-free nanostructured La0.58Sr0.4Co0.2 Fe0.8O3−δ cathode on scandium stabilized zirconia electrolyte for intermediate-temperature solid oxide fuel cells

LSCF powders with a specific surface area of 25.2 m² g⁻¹ and an average particle size of 89 nm are synthesized by the polymerizable complex method. The use of nanocrystalline LSCF powders allows the fabrication of an interlayer-free nanoporous cathode on top of an ScSZ electrolyte at a low temperature at which non-electrocatalytic secondary phases cannot form. The electrochemical performance of the interlayer-free cathode depends largely on the sintering temperature. A cathode sintered at below 750 °C lacks sufficient mechanical adhesion to the electrolyte, while the electrode surfaces are locally densified when sintered at above 800 °C. Impedance spectroscopy combined with microstructural evidence reveals that the optimum sintering temperature for LSCF is 750 °C. This avoids excess densification and grain growth, and results in the lowest polarization resistance (0.048 Ω cm² at 750 °C).     

Electrochemical binding and wiring in battery materials

Binders in battery electrodes not only provide mechanical cohesiveness during battery operation but can also affect the electrode properties via the surface modification. Using atomic force microscopy (AFM), we study the surface structuring of three binders: polyvinylidene fluoride (PVdF), carboxymethyl cellulose (CMC) and gelatin. We try to find correlation between the observed structures and the measured electrochemical charge–discharge characteristics. We further measure the binding ability of gelatin adsorbed from solutions of different pHs. While the best binding ability of gelatin is obtained at pH about 9, the least polarization is observed at pH 12. Both properties are explained based on the observed gelatin structuring as a function of pH. In the second part of this study, gelatin is used as a surface agent that dictates the organization of nanometre-sized carbon black particles around micrometre-sized cathodic active particles. Using microcontact impedance measurements on polished pellets we show that using gelatin-forced carbon black deposition the average electronic resistance around LiMn₂O₄ particles is decreased by more than two orders of magnitude. We believe that it is this decrease in resistance that improves significantly the rate performance of various cathode materials, such as LiMn₂O₄ and LiCoO₂.     

Fundamental mechanisms limiting solid oxide fuel cell durability

The fundamental issues associated with solid oxide fuel cell (SOFC) durability have been reviewed with an emphasis on general features in SOFCs and respective anode and cathode related phenomena. As general features, physicochemical properties and cell performance degradation/failure are correlated and bridged by the electrode reaction mechanisms. Particular emphasis is placed on the elemental behaviour of gaseous impurities and the possible role of liquids formed from gaseous substances. The lifetime of a state-of-the-art Ni cermet anodes is limited by a variety of microstructural changes, which mainly result from material transport-, deactivation- and thermomechanical mechanisms. Anode degradation can mainly be influenced by processing, conceptual and operating parameters. Designing a redox stable anode is currently one of the biggest challenges for small scale SOFC systems. Degradation mechanisms of different cathode materials are reviewed with a focus on the intrinsic degradation of doped lanthanum manganites (e.g. LSM) and doped lanthanum ferro-cobaltites (LSCF). Manganese-based perovskites can be regarded to be sufficiently stable, while for the better performing LSCF cathodes some intrinsic degradation was detected. New materials that are supposed to combine a better stability and high performance are also shortly mentioned.     

A Review on Metal‐Free Doped Carbon Materials Used as Oxygen Reduction Catalysts in Solid Electrolyte Proton Exchange Fuel Cells

Within the last decade, metal‐free heteroatom doped carbon nanomaterials have gained attention as effective electrocatalysts for the oxygen reduction reaction (ORR) in many electrochemical systems. Since then, reports have stated that the ORR catalytic activity, onset potential, and H₂O production selectivity of these materials is similar to that of platinum‐based catalysts. These statements rely on cyclic voltammetry (CV) and rotating disc electrode (RDE) measurements in liquid alkaline electrolyte. However, fuel cell researchers aim to replace the costly platinum catalysts in the more prominent acidic solid electrolyte proton exchange fuel cell (PEFC). In this respect, there are only a few reports of unpromising activity, stability, and H₂O production selectivity. In addition, only few reports have been presented on the implementation of such materials in cathode catalyst layers of actual PEFC devices. This mini‐review aims to summarize and evaluate results of these reports. Material synthesis, cell power, open circuit voltage, stability properties, and proposed active sites are reviewed. To date, the highest reported PEFC power densities with guaranteed metal‐free heteroatom doped carbon cathode catalysts have reached up to 321 mW cm⁻²; which although a promising value is substantially short of values obtained for platinum based catalysts.     

Reliability Evaluation of an Open‐Cathode PEMFC at Operating State and Longtime Vibration by Mechanical Loads

Reliability and durability of proton exchange membrane fuel cells (PEMFCs) are one of the most complex issues in real applications' environment. Especially, when it subjects to the various mechanical loads and vibrations. This topic requires more attention for research and experimental works. In this study, the effect of mechanical loads was investigated on an open‐cathode PEMFC in operating state. Several long time vibration tests have been applied on non‐operating PEMFC, and the performance of the fuel cell was evaluated during the test. Hydrogen leakage as a key parameter was investigated in performance monitoring instead of measuring torque on compression bolts. The vibration tests were consisted of sine, shock and random for X, Y and Z axes in operating state and random vibration in non‐operating state of PEMFC. The experimental results in operating state were indicated that the fuel cell performance has not been affected by the proposed vibrations. Furthermore, the test results of non‐operating state have been shown that the performance of PEMFC reduces about 0.6% in each four‐hour step of the vibration test. In addition, the experiments reveal that if the mechanical loads and vibrations cause physical damage on the fuel cell components, they can change the performance and reliability of the fuel cell.     

Evaluation of Using LaNi0.6Fe0.4O3–δ Contact Layer Between La0.6Sr0.4FeO3 Cathode and Crofer22APU Interconnect for Solid Oxide Fuel Cells

Interconnect‐cathode interfacial adhesion is important for the durability of solid oxide fuel cell (SOFC). Thus, the use of a conductive contact layer between interconnect and cathode could reduce the cell area specific resistance (ASR). The use of La_0.6Sr_0.4FeO₃ (LSF) cathode, LaNi_0.6Fe_0.4O_3–δ (LNF) contact layer and Crofer22APU interconnect was proposed as an alternative cathode side. LNF‐LSF powder mixtures were heated at 800 °C for 1,000 h and at 1,050 °C for 2 h and analyzed by X‐Ray power diffraction (XRD). The results indicated a low reactivity between the materials. The degradation occurring between the components of the half‐cell (LSF/LNF/Crofer22APU) was studied. XRD results indicated the formation of secondary phases, mainly: SrCrO₄, A(B, Cr)O₃ (A = La, Sr; B = Ni, Fe) and SrFe₁₂O₁₉. Scanning electron microscopy with energy dispersive X‐Ray spectroscopy (SEM‐EDX) and the X‐Ray photoelectron spectroscopy (XPS) analyzes confirmed the interaction between LSF/LNF and the metallic interconnect due to the Cr vaporization/migration. An increment of the resistance of ∼0.007 Ω cm² in 1,000 h is observed for (LSF/LNF/Crofer22APU) sample. However, the ASR values of the cell without contact coating, (LSF/Crofer22APU), were higher (0.31(1) Ω cm²) than those of the system with LNF coated interconnect (0.054(7) Ω cm²), which makes the proposed materials combination interesting for SOFC.     

锂离子电池正极材料LiNi_(0.8)Al_(0.2)O_(2-x)F_x的制备及其性能的研究

通过掺杂合成锂离子电池正极材料LiNi0.8Al0.2O2-xFx,研究了掺杂离子氟对材料性能的影响。XRD分析表明,该种材料具有层状结构,从结构上保证了该材料具有较好的嵌锂性能。SEM观察显示,材料的颗粒比较均匀。     

Crystal structure and electrochemical performance of Li3V2(PO4)3 synthesized by optimized microwave solid-state synthesis route

To investigate the crystal structure and electrochemical performance of samples synthesized under different microwave solid-state synthesis condition, a series of Li₃V₂(PO₄)₃ samples has been synthesized at five different temperatures for 3-5 min and at 750 °C for various time. The as-synthesized Li₃V₂(PO₄)₃ samples are characterized and studied by ICP-AES analysis, X-ray diffraction (XRD), Rietveld analysis, scanning and transmission electron microcopy (SEM and TEM). At relatively lower temperature (650 °C) and very short reaction time (3 min), pure phase of Li₃V₂(PO₄)₃ could be synthesized in microwave irradiation field. The crystal structure and Li atomic fractional coordinate present a significant deviation upon the change of microwave irradiation temperature and time. Relatively, the diffusion ability of lithium cations and the electrochemical performance are affected. Under the proper reaction temperature and time, the carbon-free samples MW750C5m and MW850C3m show the best specific discharge capacity 126.4 and 132 mAh g⁻¹ at the voltage range of 3.0-4.3 V, near the reversible cycling of two lithium ions per Li₃V₂(PO₄)₃ formula unit (133 mAh g⁻¹). At the voltage range of 3-4.8 V, the sample MW750C5m presents the best initial specific charge capacity of 197 mAh g⁻¹, equivalent to the reversible cycling of three lithium ions per Li₃V₂(PO₄)₃ formula unit (197 mAh g⁻¹). The initial discharge capacity, the samples MW750C5m and MW850C3m present high specific discharge capacity 183.4 and 175.7 mAh g⁻¹, respectively. The relationship among microwave irradiation condition, crystal structure, lithium atomic fractional coordinates and the electrochemical performance have been discussed in detail.     

Efficient microwave hydrothermal synthesis of nanocrystalline orthorhombic LiMnO2 cathodes for lithium batteries

Rod-like orthorhombic LiMnO₂ nanocrystals were successfully synthesized using temperature-controlled microwave hydrothermal route (TCMH) in a short time (30 min) at a temperature as low as 160 °C. o-LiMnO₂ obtained by two different methods was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemistry test. SEM revealed that the product obtained in case of TCMH was rod-like with a diameter of 40 nm, while the nanoparticles with 200 nm diameter were obtained by traditional hydrothermal route (TH). The dramatic formation of o-LiMnO₂ in the microwave hydrothermal field influenced the morphology and crystal structure of the final products. The formation and preferred growth orientation mechanism of o-LiMnO₂ in the microwave irradiation process was discussed. Electrochemistry performance exhibited that the as-synthesized o-LiMnO₂ nanorods reached the maximum discharge capacity of 194.2 mAh g⁻¹ at 0.1 C rate after several cycles between 2.2 and 4.4 V vs. Li⁺/Li at room temperature, which was higher than the electrochemical performance of o-LiMnO₂ obtained by TH. The experimental results showed that the TCMH method provided an effective way for preparing o-LiMnO₂ cathode material in lithium-ion batteries.     

Hydrothermal synthesis and rate capacity studies of Li3V2(PO4)3 nanorods as cathode material for lithium-ion batteries

It is an effective method by synthesizing one-dimensional nanostructure to improve the rate performances of cathode materials for Li-ion batteries. In this paper, Li₃V₂(PO₄)₃ nanorods were successfully prepared by hydrothermal reaction method. The structure, composition and shape of the prepared were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scan electron microscope (SEM) and transmission electron microscope (TEM), respectively. The data indicate the as-synthesis powders are defect-rich nanorods and the sizes are the length of several hundreds of nanometers to 1 μm and the diameter of about 60 nm. The preferential growth direction of the prepared material was the [1 2 0]. The electrodes consisting of the Li₃V₂(PO₄)₃ nanorods show the better discharge capacities at high rates over a potential range of 3.0-4.6 V. These results can be attributed to the shorter distance of electron transport and the fact that ion diffusion in the electrode material is limited by the nanorod radius. All these results indicate that the resulting Li₃V₂(PO₄)₃ nanorods are promising cathode materials in lithium-ion batteries.