The direct utilization of steelmaking by-product gases in solid oxide fuel cells (SOFCs) offers a promising pathway to improve energy efficiency and reduce carbon emissions in the steel industry. In this study, a Sr-deficient and Ni-doped double perovskite oxide, Sr1.95Fe1.35Ni0.15Mo0.5O6-δ (SFNM), was investigated as an anode material for direct Linz-Donawitz converter gas (LDG)-fueled SOFCs. A single-phase double perovskite structure was successfully obtained after calcination at 1,200°C for 12 h, while exsolved metallic Ni nanoparticles were generated on the SFNM surface after reduction at 800°C. Electrochemical performance was evaluated using H2, simulated-LDG, and CO/CO2 (85:15) fuels at 800°C. The maximum power densities achieved were 1.23, 0.70, and 0.40 W cm-2 for H2, simulated-LDG, and CO/CO2 fuels, respectively. Although CO-containing fuels exhibited lower opencircuit voltages and power outputs than H2, the SFNM anode maintained stable operation and appreciable performance under direct simulated-LDG utilization. Impedance analysis revealed that the increased polarization resistance in simulated-LDG and CO/CO2 atmospheres was mainly associated with fuel adsorption/desorption and gas diffusion, while interfacial charge-transfer resistance remained relatively small. The superior performance obtained with simulated-LDG compared to the CO/CO2 mixture was attributed to the presence of a small amount of H2, which facilitated anode reaction kinetics. These results demonstrate that SFNM is a promising mixed ionic-electronic conductor anode for the direct electrochemical conversion of CO-rich steelmaking by-product gases into electricity.
Lithium-ion batteries (LIBs) have attracted great attention as the common power source in energy storage fields of large-scale applications such as electrical vehicles (EVs), industries, power plants, and grid-scale energy storage systems (ESSs). Insertion, alloying, and conversion reactions are the main electrochemical energy storage mechanisms in LIBs, which determine their electrochemical properties and performances. The electrochemical reaction mechanisms are determined by several factors including crystal structure, components, and composition of electrode materials. This article reviews a new strategy to compensate for the intrinsic shortcomings of each reaction mechanism by introducing the material systems to form a single compound with different types of reaction mechanisms and to allow the simultaneous hybrid electrochemical reaction of two different mechanisms in a single solid solution phase.
Herein we investigated the effect of the conductive agent on the electrochemical performance of the SiOx anode. SiOx anodes have a relatively low volume expansion (~160%) compared to Pure-silicon, but have a problem in that they have a poor electrical conductivity characteristic. In this study, physical and electrochemical measurements were performed using two 0-dimensional amorphous carbon conductive agents with different crystallinity and surface area. The crystal structure of the conductive agents and the local graphitization degree were analyzed through XRD and Raman, and the surface area of the particles was observed through BET. In addition, the electrical performance according to the graphitization degree of the conductive agents was confirmed through a 4-point probe. As a result of the electrochemical cycle and rate performance, it was confirmed that the performance of SiOx using a conductive agent having a low graphitization degree and a high surface area was improved. The results in this study suggest that the graphitization degree and surface area of the amorphous carbon conductive agent may play an important role in the SiOx electrode.
The carbonaceous materials have attracted much attention for utilization of anode materials for lithium-ion batteries. Among them, hollow carbon spheres have great advantages (high specific capacity and good rate capability) to replace currently used graphite anode materials, due to their unique features such as high surface areas, high electrical conductivities, and outstanding chemical and thermal stability. Herein, we have synthesized various sizes of hollow carbon spheres by a facile hard-template method and investigated the anode properties for lithium-ion batteries. The obtained hollow carbon spheres have uniform diameters of 350 ~ 600 nm by varying the template condition, and they do not have any cracks after the optimization of the process. Increasing the diameter of hollow carbon spheres decreases their specific capacities, since the larger hollow carbon spheres have more useless spaces inside that could have a disadvantage for lithium storage. The hollow carbon spheres have outstanding rate and cyclic performance, which is originated from the high surface area and high electrical properties of the hollow carbon spheres. Therefore, hollow carbon spheres with smaller diameters are expected to have higher specific capacities, and the noble channel structures through various doping approaches can give the great possibility of high lithium storage properties.
In order to increase the electrochemical performance of thermal battery anode, LIFT anode having the same weight but a larger lithium content in electrodes was fabricated by mixing lithium, iron and titanium. By applying these electrodes, a single cell and a thermal battery were prepared, and the effect of LIFT anode on electrochemical performance was evaluated. The LIFT-applied single cell presented a better cell performance than LIFe-applied single cell at 500℃ and 550℃. The discharge performance of LIFT-applied single cell, which included the operating time (787s), specific capacity (1,683 Asg-1), and electrode utilization (80.7%), was improved collectively compared to the LIFe applied single cell (736s, 1,245 As g-1, and 74.6%) at 500℃. As the discharge progressed, the internal resistance of LIFT anode decreased, because the lithium migration path was formed due to the presence of large titanium particles among iron particles. These results were analyzed in terms of the microstructure of electrode using SEM. Energy density of LIFT-applied single cell also increased by 10% to 142.1 Wh kg-1 compared to that of LIFe-applied single cell (127.4 Wh kg-1). In addition, the LIFT-applied single cell presented a stable discharge performance for 6,500s without a short circuit which could occur by molten lithium under an open circuit voltage condition with a high pressure (4 kgf cm-2). As observed in the high temperature thermal battery performance tests, the voltage and specific capacity of LIFTapplied thermal battery are superior to those of LIFe-applied thermal batteries, indicating that the energy density of LIFT-applied thermal batteries should remarkably increase.
This paper reports the microstructure and electrochemical properties of Si-Al-Fe ternary amorphous alloys prepared by rapid solidification as an anode for lithium secondary batteries. The microstructure was analyzed using XRD and HR-TEM with EDS mapping. In accordance with DSC analysis, annealing was performed to crystallize the active nano-Si in the amorphous alloy. Thus, nano-Si forms (~80 nm) embedded in the matrix alloy, such as Fe2Al3Si3, FeSi2, and Fe0.42Si2.67, were successfully synthesized. The electrode based on the Si-Al-Fe ternary alloy delivered an initial discharge capacity of approximately 700 mAh g-1, and exhibited a high Coulombic efficiency of 99.0~99.6% from the 2nd to 70th cycles.
Black phosphorus (BP) is a potential candidate for an anode in lithium ion batteries due to its high theoretical capacity and the large interlayer spacing in the monolayered phosphorene form, allowing for lithium intercalation/ deintercalation. In this study, large-scale exfoliation of bulk BP was accomplished using a solution of NaOH and N-methyl-2-pyrrolidone (NMP), yielding phosphorene, which can be assembled into nanoflakes using electrophoretic deposition (EPD). Through the systematic addition of NaOH and subsequent sonication, BP nanoflakes were obtained in high yields by EPD, allowing for the integration of these nanoflakes into an anode in the film state. Anodes with a charge/discharge capacity of 172 mAh/g at a rate of 200 mA/g were obtained, which are promising for battery applications through various post-film treatments.
This work investigated the effects of different conductive agents on the electrochemical properties of anodes. SiOx possesses high theoretical capacity and shows excellent cycle performance; however, the low initial coulombic efficiency and poor electrical conductivity limit its applications in real batteries. In this study, electrodes were fabricated using two different conductive agents, and the resulting physical and electrochemical properties were analyzed. SEM observations confirmed the formation of a CNT conductive network throughout the electrodes, while the electrical conductivity contributed to the electrode was confirmed by impedance measurements. Thus, the electrode fabricated with the CNT conductive agent showed greater capacity and superior cycle performance than did the electrode fabricated using the DB conductive agent.
Lithium anodes (13, 15, 17, and 20 wt% Li) were fabricated by mixing molten lithium and iron powder, which was used as a binder to hold the molten lithium, at about 500℃ (discharge temp.). In this study, the effect of applied pressure and lithium content on the discharge properties of a thermal battery’s single cell was investigated. A single cell using a Li anode with a lithium content of less than 15 wt% presented reliable performance without any abrupt voltage drop resulting from molten lithium leakage under an applied pressure of less than 6 kgf/㎠. Furthermore, it was confirmed that even when the solid electrolyte is thinner, the Li anode of the single cell normally discharges well without a deterioration in performance. The Li anode of the single cell presented a significantly improved open-circuit voltage of 2.06 V, compared to that of a Li-Si anode (1.93 V). The cut-off voltage and specific capacity were 1.83 V and 1,380 As g-1 (Li anode), and 1.72 V and 1,364 As g-1 (Li-Si anode). Additionally, the Li anode exhibited a stable and flat discharge curve until 1.83 V because of the absence of phase change phenomena of Li metal and a subsequent rapid voltage drop below 1.83 V due to the complete depletion of Li at the end state of discharge. On the other hand, the voltage of the Li-Si anode cell decreased in steps, 1.93 V → 1.72 V (Li13Si4 → Li7Si3) → 1.65 V (Li7Si3→ Li12Si7), according to the Li-Si phase changes during the discharge reaction. The energy density of the Li anode cell was 807.1 Wh l-1, which was about 50% higher than that of the Li-Si cell (522.2 Wh l-1).
Transition metal oxide materials have attracted widespread attention as Li-ion battery electrode materials owing to their high theoretical capacity and good Li storage capability, in addition to various nanostructured materials. Here, we fabricated a CoO Li-ion battery in which Co nanoparticles (NPs) are deposited into a current collector through electrophoretic deposition (EPD) without binding and conductive agents, enabling us to focus on the intrinsic electrochemical properties of CoO during the conversion reaction. Through optimized Co NP synthesis and electrophoretic deposition (EPD), CoO Li-ion battery with 630 mAh/g was fabricated with high cycle stability, which can potentially be used as a test platform for a fundamental understanding of conversion reaction.
Nanomaterials have considerable potential to solve several key challenges in various electrochemical devices, such as fuel cells. However, the use of nanoparticles in high-temperature devices like solid-oxide fuel cells (SOFCs) is considered problematic because the nanostructured surface typically prepared by deposition techniques may easily coarsen and thus deactivate, especially when used in high-temperature redox conditions. Herein we report the synthesis of a self-regenerated Pd metal nanoparticle on the perovskite oxide anode surface for SOFCs that exhibit self-recovery from their degradation in redox cycle and CH4 fuel running. Using Pd-doped perovskite, La(Sr)Fe(Mn, Pd)O3, as an anode, fairly high maximum power densities of 0.5 and 0.2 cm-2 were achieved at 1,073 K in H2 and CH4 respectively, despite using thick electrolyte support-type cell. Long-term stability was also examined in CH4 and the redox cycle, when the anode is exposed to air. The cell with Pd-doped perovskite anode had high tolerance against re-oxidation and recovered the behavior of anodic performance from catalytic degradation. This recovery of power density can be explained by the surface segregation of Pd nanoparticles, which are self-recovered via re-oxidation and reduction. In addition, self-recovery of the anode by oxidation treatment was confirmed by X-ray diffraction (XRD) and scanning electron microscopy (SEM).
A layered planer SOFC module was designed from planar-type SOFC. It was prepared by multi-layered ceramic technology. To form the cathode and the anode in the layered structure, reliable channels should be made on the both side of electrolyte perpendicularly. However, monolithic SOFC using multi-layered ceramic technology hasn`t been studied another group, and the warpage of electrolyte in the channel, also, hasn`t been studied, when electrode is printed on the electrolyte. In this study, the channels are prepared with electrode printing, and their warpage are evaluated. In the case of YSZ without electrode, the warpages are nothing in the limit of measurement using optical microscope. The warpage of ``YSZ-NiO printed`` increases than that of ``NiO printed``, and also, the case of ``double electrode printed`` is similar to ``YSZ-NiO printed``. It is thought that, in the printed electrolyte, the warpage is related to the difference of the sintering behavior of each material.
In this study, magnesium (Mg), zinc (Zn) and aluminium (Al) as anode electrode and the solution of NaCl dissolved with 2~20 wt% as electrolytes were used for the metal-air cell. The open circuit voltage, short circuit current and I-V characteristics upon different kinds of anode electrode and electrolyte concentration were investigated. The open circuit voltage, initially about 1.45 V, rises to 1.6 V during the first 10 minutes indicating the necessity of an induction time to activate the catalyst on the air cathode. The short circuit current increases with an increased concentration of NaCl, causes an increase in the conductivity of the electrolyte solution, but the open circuit voltage did not under undergo influence of electrolyte. From NaCl 20 wt% electrolyte, the maximum output power of the magnesium electrode materials was measured with 177mW. It is found that the power characteristics of metal-air cell could be improved by using magnesium electrode materials in the NaCl electrolyte.
Three-dimensionally ordered macro-porous Sn-C composites were prepared by using polystyrene microsphere as a template. The Sn-C composites were composed of well-interconnected pore with circular shape and wall structure with wall thickness of a few tens of nano-meters. This porous three-dimensional structure is readily and uniformly accessible to the electrolyte, which facilitates lithium ion diffusion during charge-discharge reactions. The wall thickness of the composites was increased as the increase of Sn content of the composite. From EDS analysis, it is confirmed that the Sn was dispersed uniformly in Sn-C composites. The capacity was increased as the Sn content increased, which is due to Sn anode with high capacity. The Sn-C composites with high Sn content showed superior cyclic performances. Such enhancement is ascribed to the thick wall thickness and small pore size of the sample with high Sn content. The Sn-C composite with Sn 30 wt% showed relatively high capacity and stable cycle life, however, the stability of the 3-dimensional structure should be enhanced by further work.