• Nuclear Engineering and Technology
• /
• v.28 no.2
• /
• pp.118-128
• /
• 1996

The lattice parameters of stoichiometric $UO_2$ and $U_{1-y}Er_{y}O_2$ in the range of y=0.01 to y =0.33 were determined with use of X-ray diffraction data. Oxygen potentials have been measured by means of a thermogravimetric method in the range of 1200~$1500^{\circ}C$ and $10^{-14}$ $\leq$ $Po_2$ $\leq$ $10^{-3}$ for pure $UO_2$ and $U_{1-y}Er_{y}O_{2{\pm}x}$ solid solutions with y=0.02, y=0.06 and y=0.20, respectively. Their oxygen partial pressures were maintained by controlling $CO_2$/CO mixture atmosphere, and the $Po_2$ values corresponding to x of $U_{1-y}Er_{y}O_{2{\pm}x}$ solid solutions were measured with an electrolyte oxygen sensor. The lattice parameter decreases linearly with an increase in the erbium content. The change of the lattice parameter can be expressed in a linear equation of y as a($\AA$) =5.4695-0.220y for 0 $\leq$y$\leq$0.33. The experimental coefficient of y -0.220 in $U_{1-y}Er_{y}O_2$ was an intermediate value between the calculated values -0.273 and -0.156 in the case of $U^{5+}$ and $U^{6+}$, respectively. The (equation omitted) has been found to undergo abrupt increase in the range of -360 to -270 kJ/mole for y=0.06 and -320 to -220 H/mole for y=0.20, respectively, in the temperature range of 1200-$1500^{\circ}C$. (equation omitted) increases with erbium content, but the effect of the dopant for x =0.01 is less significant than that for stoichiometry. The oxygen potentials for $UO_2$ and $U_{0.98}Er_{0.02}O_{2+x}$ can be approximately represented by the $U^{5+}$/$U^{4+}$ model but those for y$\geq$ 0.06 in $U_{1-y}Er_{y}O_{2{\pm}x}$ solid solutions cannot be interpreted by the mean uranium valence model.

• Korean Chemical Engineering Research
• /
• v.59 no.4
• /
• pp.557-564
• /
• 2021

Sr_0.92Y_0.08Ti_1-xV_xO_3-δ (SYTV) with perovskite structure was investigated as an alternative anode to utilize H₂S containing fuels in solid oxide fuel cells. To improve the electrochemical performance of Sr_0.92Y_0.08TiO_3-δ (SYT), vanadium(V) was substituted to titanium(Ti) at the B-site of the SYT perovskites. The SYTV synthesized by the Pechini method was chemically compatible with the YSZ electrolyte without additional by-products formation under the cell fabricating conditions. As increasing V substitution amounts, the oxygen vacancies increased, resulting to increasing ionic conductivity of the anode. The cell performance in pure H₂ at 850 ℃ is 19.30 mW/cm² and 34.87 mW/cm² for a 1 mol.% and 7 mol.% of V substituted anodes, respectively. The cell performance using H₂ fuel containing 1000 ppm of H₂S at 850 ℃ was 23.37 mW/cm² and 73.11 mW/cm² for a 1 mol.% and 7 mol.% of V substituted anodes, respectively.

• Journal of the Korean Electrochemical Society
• /
• v.1 no.1
• /
• pp.1-7
• /
• 1998

For the purpose of finding new cathode materials for medium-temperature $(700\~800^{\circ}C)$ solid oxide fuel cells, $Gd_{0.8}Ca_{0.2}Co_{1-x}Fe_xO_3,\;(x=0.0\~0.5)$ are prepared, and their thermal stability and conductivity characteristics are investigated. Also, the cathodic activities are measured after the cathode layer being attached on CGO (cerium-gadolinium oxide) electrolyte disk. The X-ray analyses indicate that the materials prepared by calcining the citrate-gels at $800^{\circ}C$ have the orthorhombic perovskite structure without discernible impurities. The thermal stability of the undoped Co perovskite is so poor that it is decomposed to the individual binary oxide even at $1300^{\circ}C$. But the partially Fe-doped cobaltates exhibit a better thermal stability to retain their structural integrity up to $1400^{\circ}C$. The observation whereby both the undoped and Fe-doped cobaltates melt at ca. $1300^{\circ}C$ leads us to perform the electrode adhesion at <$1300^{\circ}C$. The cathodic activity of $Gd_{0.8}Ca_{0.2}Co_{1-x}Fe_xO_3,\;(x=0.0\~0.5)$, electrodes is superior to $La_{0.9}Sr_{0.1}MnO_3$, among the samples of $x=0.0\~0.5$, the x=0.2 cathode shows the best activity for the oxygen reduction reaction. It is likely that the Fe-doping provides a better thermal stability to the materials but in turn imparts an inferior cathodic activity, such that the optimum trade-off is made at x=0.2 between the two factors. The total electrical conductivity and ion conductivity of $Gd_{0.8}Ca_{0.2}Co_{1-x}Fe_xO_3$, are measured to be 51 S/cm and $6.0\times10^{-4}S/cm\;at\;800^{\circ}C$, respectively. The conductivity values illustrate that the materials are a mixed conductor and the reaction sites can be expanded to the overall electrode surface, thereby providing a better cathodic activity than $La_{0.9}Sr_{0.1}MnO_3$.

• Journal of the Korean Electrochemical Society
• /
• v.10 no.4
• /
• pp.283-287
• /
• 2007

KIER has been developing the anode-supported flat tubular solid oxide fuel cell unit bundle for the intermediate temperature($700{\sim}800^{\circ}C$) operation. Anode-supported flat tubular cells have Ni/YSZ cermet anode support, 8 moi.% $Y_2O_3$ stabilized $ZrO_2(YSZ)$ thin electrolyte, and cathode multi-layer composed of Sr-doped $LaSrMnO_3(LSM)$, LSM-YSZ composite, and $LaSrCoFeO_3(LSCF)$. The prepared anode-supported flat tubular cell was joined with ferritic stainless steel cap by induction brazing process. Current collection for the cathode was achieved by winding Ag wire and $La_{0.6}Sr_{0.4}CoO_3(LSCo)$ paste, while current collection for the anode was achieved by using Ni wire and felt. For making stack, the prepared anode-supported flat tubular cells with effective electrode area of $90\;cm^2$ connected in series with 12 unit bundles, in which unit bundle consists of two cells connected in parallel. The performance of unit bundle in 3% humidified $H_2$ and air at $800^{\circ}C$ shows maximum power density of $0.39\;W/cm^2$ (@ 0.7V). Through these experiments, we obtained basic technology of the anode-supported flat tubular cell and established the proprietary concept of the anode-supported flat tubular cell unit bundle.

• Journal of the Korean Electrochemical Society
• /
• v.4 no.2
• /
• pp.58-64
• /
• 2001

YSZ ($8mol\%$ yttria-stabilized zirconia)-modified LSM $(La_{0.85}Sr_{0.15}MnO_3)$ composite cathodes were fabricated by formation of YSZ film on triple phase boundary (TPB) of LSM/YSZ/gas. The YSZ coating film greatly enlarged electrochemical reaction sites from the increase of additional TPB. The composite cathode was formed on thin YSZ electrolyte (about 30 Um thickness) supported on an anode and then I-V characterization and AC impedance analyses were performed at temperature between $700^{\circ}C\;and\;800^{\circ}C$. As results of the impedance analysis on the cell at $800^{\circ}C$ with humidified hydrogen as the fuel and air as the oxidant, R1 around the frequency of 1000 Hz represents the anode Polarization. R2 around the frequency of 100Hz indicates the cathode polarization, and R3 below the frequency of 10 Hz is the resistance of gas phase diffusion through the anode. The cell with the composite cathode produced power density of $0.55\;W/cm^2\;and\;1W/cm^2$ at air and oxygen atmosphere, respectively. The I-V curve could be divided into two parts showing distinctive behavior. At low current density region (part I) the performance decreased steeply and at high current density region (part II) the performance decreased gradually. At the part I the performance decrease was especially resulted from the large cathode polarization, while at the part H the performance decrease related to the electrolyte polarization.

• Journal of the Korean Electrochemical Society
• /
• v.20 no.1
• /
• pp.7-12
• /
• 2017

Using a precursor of $LiNi_{0.6}Co_{0.2}Mn_{0.2}O_2$ as a starting material, a surface-modified cathode material was obtained by coating with KCl, where the added KCl reduces residual Li compounds such as $Li_2CO_3$ and LiOH, on the surface. The resulting electrochemical properties were investigated. The amounts of $Li_2CO_3$ and LiOH decreased from 8,464 ppm to 1,639 ppm and from 8,088 ppm to 6,287 ppm, respectively, with 1 wt% KCl added $LiNi_{0.6}Co_{0.2}Mn_{0.2}O_2$ that had been calcined at $800^{\circ}C$. X-ray diffraction results revealed that 1 wt% of KCl added $LiNi_{0.6}Co_{0.2}Mn_{0.2}O_2$ did not affect the parent structure but enhanced the development of hexagonal crystallites. Additionally, the charge transfer resistance ($R_{ct}$) decreased dramatically from $225{\Omega}$ to $99{\Omega}$, and the discharge capacity increased to 182.73mAh/g. Using atomic force microscopy, we observed that the surface area decreased by half because of the exothermic heat released by the Li residues. The reduced surface area protects the cathode material from reacting with the electrolyte and hinders the development of a solid electrolyte interphase (SEI) film on the surface of the oxide particles. Finally, we found that the introduction of KCl into $LiNi_{0.6}Co_{0.2}Mn_{0.2}O_2$ is a very effective method of enhancing the electrochemical properties of this active material by reducing the residual Li. To the best of our knowledge, this report is the first to demonstrate this phenomenon.

• Korean Chemical Engineering Research
• /
• v.50 no.4
• /
• pp.749-753
• /
• 2012

In present work, anode support for micro-tubular SOFC was fabricated with outer diameter of 3 mm and characterized with microstructure, mechanical properties and gas permeability. The microstructure of surface and cross section of a porous anode support were analyzed by using SEM (Scanning Electron Microscope) image. The gas permeability and the mechanical strength of anode support was measured and analysed by using differential pressure at the flow rates of 50, 100, 150 cc/min. and using universal testing machine respectively. The unit cell composed of NiO-YSZ, YSZ, YSZ-LSM/LSM/LSCF was fabricated and operated with reaction temperature and fuel flow rate and showed maximum power density of $1095mW/cm^2$ on the condition of $800^{\circ}C$. The performance of single cell for micro-tubular SOFC increased with the increasing the reaction temperature due to the decrement of ohmic resistance of cell by the increment of the ionic conductivity of electrolyte through the evaluation of electrochemical impedance analysis for single cell with reaction temperature.

• 한국신재생에너지학회:학술대회논문집
• /
• 2010.06a
• /
• pp.89.1-89.1
• /
• 2010

Since Gratzel and co-workers developed a new type of solar cell based on the nanocrystalline $TiO_2$ electrode, dye-sensitized solar cells (DSSCs) have attracted considerable attention on account of their high solar energy-to-conversion efficiencies (11%), their easy manufacturing process with low cost production compared to conventional p-n junction solar cells. The mechanism of DSSC is based on the injection of electrons from the photoexcited dye into the conduction band of nanocrystalline $TiO_2$. The oxidized dye is reduced by the hole injection process from either the hole counter or electrolyte. Thus, the electronic structures, such as HOMO, LUMO, and HOMO-LUMO gap, of dye molecule in DSSC are deeply related to the electron transfer by photoexcitation and redox potential. To date, high performance and good stability of DSSC based on Ru-dyes as a photosensitizer had been widely addressed in the literatures. DSSC with Ru-bipyridyl complexes (N3 and N719), and the black ruthenium dye have achieved power conversion efficiencies up to 11.2% and 10.4%, respectively. However, the Ru-dyes are facing the problem of manufacturing costs and environmental issues. In order to obtain even cheaper photosensitizers for DSSC, metal-free organic photosensitizers are strongly desired. Metal-free organic dyes offer superior molar extinction coefficients, low cost, and a diversity of molecular structures, compared to conventional Ru-dyes. Recently, novel photosensitizers such as coumarin, merocyanine, cyanine, indoline, hemicyanine, triphenylamine, dialkylaniline, bis(dimethylfluorenyl)-aminophenyl, phenothiazine, tetrahydroquinoline, and carbazole based dyes have achieved solar-to-electrical power conversion efficiencies up to 5-9%. On the other hand, organic dye molecules have large ${\pi}$-conjugated planner structures which would bring out strong molecular stacking in their solid-state and poor solubility in their media. It was well known that the molecular stacking of organic dyes could reduce the electron transfer pathway in opto-electronic devices, significantly. In this paper, we have studied on synthesis and characterization of dendritic organic dyes with different number of electron acceptor/anchoring moieties in the end of dendrimer. The photovoltaic performances and the incident photon-to-current (IPCE) of these dyes were measured to evaluate the effects of the dendritic strucuture on the open-circuit voltage and the short-circuit current.

• 한국신재생에너지학회:학술대회논문집
• /
• 2010.06a
• /
• pp.64.1-64.1
• /
• 2010

The morphology of mesoporous $TiO_2$ films plays an important role in the operation of a DSSC. For example, the energy conversion efficiency of DSSCs with well-organized mesoporous $TiO_2$ films is much higher than those with traditional films possessing a random morphology. In previous research, well-organized mesoporous $TiO_2$ films have mainly been synthesized using an amphiphilic block copolymer, e.g., a poly(ethylene oxide) (PEO)-based template. A graft copolymer is more attractive than a block copolymer due to its low cost and the ease with which it can be synthesized. In this work, we provide the first report on the successful synthesis of well-organized mesoporous $TiO_2$ films templated by an organized graft copolymer as a structure directing agent. Well-organized mesoporous $TiO_2$ films with excellent channel connectivities were developed via the sol gel processusing an organized PVC-g-POEM graft copolymer synthesized by one-pot ATRP. The careful adjustment of copolymer composition and solvent affinity using a THF/$H_2O$/HCl mixture was used to systematically vary the material structure. The influence of the material structure on solar cell performance was then investigated. A solid-state DSSC employing both the graft copolymer templated organized 700 nm-thick $TiO_2$ films and graft copolymer electrolytes exhibited a solar conversion efficiency of 2.2% at 100 $mW/cm^2$. This value was approximately two-fold higher than that attained from a DSSC employing a random mesoporous $TiO_2$ film. The solar cell performance was maximized at 4.6% when the film thickness was increased to $2.5{\mu}m$. We believe that this graft copolymer-directed approach introduces a new and simple route toward the synthesis of well-organized metal oxide films as an alternative to a conventional block copolymer-based template.

• 한국신재생에너지학회:학술대회논문집
• /
• 2005.06a
• /
• pp.306-309
• /
• 2005

One of the most critical issues in sol id oxide fuel cell (SOFC)running on hydrocarbon fuels is the risk of carbon formation from the fuel gas. The simple method to reduce the risk of carbon formation from the reactions is to add steam to the fuel stream, leading to the carbon gasification react ion. However, the addition of steam to fuel is not appropriate for the auxiliary power unit (APU) and potable power generation (PPG) systems due to an increase of complexity and bulkiness. In this regard, many researchers have focused on so-called 'direct methane' operation of SOFC, which works with dry methane without coking. However, coking can be suppressed only by the operation with a high current density, which may be a drawback especially for the APU and PPG systems. The single chamber fuel cell (SC-SOFC) is a novel simplification of the conventional SOFC into which a premixed fuel/air mixture is introduced. It relies on the selectivity of the anode and cathode catalysts to generate a chemical potential gradient across the cell. Moreover it allows compact and seal-free stack design. In this study, we fabricated honeycomb type mixed-gas fuel cell (MGFC) which has advantages of stacking to the axial direction and increasing volume power density. Honeycomb-structured SOFC with four channels was prepared by dry pressing method. Two alternative channels were coated with electrolyte and cathode slurry in order to make cathodic reaction sites. We will discuss that the anode supported honeycomb type cell running on mixed gas condition.