• 한국분말재료학회지
• /
• 제21권5호
• /
• pp.360-365
• /
• 2014

$SnO_2-CoO$/carbon-coated CoO core/shell nanowire composites were synthesized by using electrospinning and hydrothermal methods. In order to obtain $SnO_2-CoO$/carbon-coated CoO core/shell nanowire composites, $SnO_2-Co_3O_4$ nanowire composites and $SnO_2-Co_3O_4$/polygonal $Co_3O_4$ core/shell nanowire composites are also synthesized. To demonstrate their structural, chemical bonding, and morphological properties, field-emission scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy were carried out. These results indicated that the morphologies and structures of the samples were changed from $SnO_2-Co_3O_4$ nanowires having cylindrical structures to $SnO_2-Co_3O_4/Co_3O_4$ core/shell nanowires having polygonal structures after a hydrothermal process. At last, $SnO_2-CoO$/carbon-coated CoO core/shell nanowire composites having irregular and high surface area are formed after carbon coating using a polypyrrole (PPy). Also, there occur phases transformation of cobalt phases from $Co_3O_4$ to CoO during carbon coating using a PPy under a argon atmosphere.

• 한국분말재료학회지
• /
• 제25권4호
• /
• pp.296-301
• /
• 2018

In this study, an experiment is performed to recover the Li in $Li_2CO_3$ phase from the cathode active material NMC ($LiNiCoMnO_2$) in waste lithium ion batteries. Firstly, carbonation is performed to convert the LiNiO, LiCoO, and $Li_2MnO_3$ phases within the powder to $Li_2CO_3$ and NiO, CoO, and MnO. The carbonation for phase separation proceeds at a temperature range of $600^{\circ}C{\sim}800^{\circ}C$ in a $CO_2$ gas (300 cc/min) atmosphere. At $600{\sim}700^{\circ}C$, $Li_2CO_3$ and NiO, CoO, and MnO are not completely separated, while Li and other metallic compounds remain. At $800^{\circ}C$, we can confirm that LiNiO, LiCoO, and $Li_2MnO_3$ phases are separated into $Li_2CO_3$ and NiO, CoO, and MnO phases. After completing the phase separation, by using the solubility difference of $Li_2CO_3$ and NiO, CoO, and MnO, we set the ratio of solution (distilled water) to powder after carbonation as 30:1. Subsequently, water leaching is carried out. Then, the $Li_2CO_3$ within the solution melts and concentrates, while NiO, MnO, and CoO phases remain after filtering. Thus, $Li_2CO_3$ can be recovered.

• 대한환경공학회지
• /
• 제27권3호
• /
• pp.253-261
• /
• 2005

불균일 $CoO_x/TiO_2$ 촉매가 충진된 연속 흐름식 고정층 반응기 내에서 ppm 수준으로 수중에 존재하는 trichloroethylene (TCE) 제거반응을 수행하였으며, 가장 우수한 반응활성을 갖는 촉매의 결정구조와 표면화학적 특성을 분석함으로써 반응시간에 따라 분해활성이 전이영역을 보이는 원인을 규명하고자 하였다. $36^{\circ}C$의 반응온도에서 모델반응의 내부확산저항은 없었으며, $TiO_2$ 표면에 흡착에 의한 액상 TCE 제거정도는 무시할 수 있었다. 5% $CoO_x/TiO_2$ 촉매는 본 대상반응에 대하여 가장 우수한 활성을 갖는 것으로 나타났으며, 반응시간의 경과정도에 따라 TCE 분해효율이 점진적으로 증가하여 안정화되는 전이영역의 존재를 확인할 수 있었다. 반응 전 5% $CoO_x$ 촉매에 대한 XRD 패턴에서 담지체로 사용된 $TiO_2$에 의한 피크들 외에 새로운 피크가 관찰되었고, 5시간 이상 동안 반응한 후에 건조된 촉매의 경우에도 반응 전 촉매의 XRD 피크와 매우 유사하였다. $Co_3O_4$의 XRD 패턴들과 대조한 결과, 5% $CoO_x$ 촉매상에서 Co 화합물에 의해 야기되는 XRD 피크들은 $Co_3O_4$에 의한 것임을 알 수 있었다. 반응물에 노출되지 않은 5% $CoO_x/TiO_2$ 촉매에 대한 XPS 측정은 797.1 eV에서 Co $2p_{1/2}$에 대한 주피크와 함께 781.3 eV에서 Co $2p_{3/2}$에 대한 주피크가 관찰되어졌다. 반응 후 촉매의 경우에는 Co $2p_{3/2}$ 및 Co $2p_{1/2}$의 binding energy들은 각각 780.3과 795.8 eV에서 나타났다. 반응 전 후 촉매상에서 Co $2p_{3/2}$의 binding energy 차이는 1.0 eV이고, Co $2p_{1/2}$의 binding energy 차이는 1.3 eV이다. 표준 $Co_3O_4$에 대한 XPS 측정결과, 반응 후 촉매상에 존재하는 $CoO_x$는 $Co_3O_4$로 존재하고, 반응 전의 경우에는 이와는 다른 chemical state를 보여주었다. XRD 및 XPS 결과를 바탕으로, 촉매표면에 존재하는 $Co_3O_4$의 외부표면이 $Co_2TiO_4$와 $CoTiO_3$ 같은 $CoTiO_x$로 encapsulation되어 있는 모델구조를 제안할 수 있고, 이는 반응시간의 함수로 나타나는 촉매활성에 있어서 전이영역의 존재를 잘 설명할 수 있을 뿐만 아니라, XRD와 XPS에서 얻어진 촉매의 물리화학적인 특성을 잘 반영할 수 있다.

• 한국환경과학회지
• /
• 제17권8호
• /
• pp.933-941
• /
• 2008

The formation of $Co_nTiO_{n+2}$ compounds, i.e., $CoTiO_3$ and $CO_2TiO_4$, in a 5wt% $CoO_x/TiO_2$ catalyst after calcination at different temperatures has been characterized via scanning electron microscopy (SEM), Raman and X-ray photoelectron spectroscopy (XPS) measurements to verify our earlier model associated with $CO_3O_4$ nanoparticles present in the catalyst, and laboratory-synthesized $Co_nTiO_{n+2}$ chemicals have been employed to directly measure their activity profiles for CO oxidation at $100^{\circ}C$. SEM measurements with the synthetic $CoTiO_3$ and $CO_2TiO_4$ gave the respective tetragonal and rhombohedral morphology structures, in good agreement with the earlier XRD results. Weak Raman peaks at 239, 267 and 336 $cm^{-1}$ appeared on 5wt% $CoO_x/TiO_2$ after calcination at $570^{\circ}C$ but not on the catalyst calcined at $450^{\circ}C$, and these peaks were observed for the $Co_nTiO_{n+2}$ compounds, particularly $CoTiO_3$. All samples of the two cobalt titanate possessed O ls XPS spectra comprised of strong peaks at $530.0{\pm}0.1$ eV with a shoulder at a 532.2-eV binding energy. The O ls structure at binding energies near 530.0 eV was shown for a sample of 5 wt% $CoO_x/TiO_2$, irrespective to calcination temperature. The noticeable difference between the catalyst calcined at 450 and $570^{\circ}C$ is the 532.2 eV shoulder which was indicative of the formation of the $Co_nTiO_{n+2}$ compounds in the catalyst. No long-life activity maintenance of the synthetic $Co_nTiO_{n+2}$ compounds for CO oxidation at $100^{\circ}C$ was a good vehicle to strongly sup port the reason why the supported $CoO_x$ catalyst after calcination at $570^{\circ}C$ had been practically inactive for the oxidation reaction in our previous study; consequently, the earlier proposed model for the $CO_3O_4$ nanoparticles existing with the catalyst following calcination at different temperatures is very consistent with the characterization results and activity measurements with the cobalt titanates.

• 한국환경과학회지
• /
• 제16권12호
• /
• pp.1431-1437
• /
• 2007

Cobalt titanates($CoTiO_x$), such as $CoTiO_3$ and $Co_2TiO_4$, have been synthesized via a solid-state reaction and characterized using X-ray diffraction(XRD) and X-ray photoelectron spectroscopic(XPS) measurement techniques, prior to being used for continuous wet trichloroethylene(TCE) oxidation at $36^{\circ}C$, to support our earlier chemical structure model for Co species in 5 wt% $CoO_x/TiO_2$(fresh) and(spent) catalysts. Each XRD pattern for the synthesized $CoTiO_3$ and $Co_2TiO_4$ was very close to those obtained from the respective standard XRD data files. The two $CoTiO_x$ samples gave Co 2p XPS spectra consisting of very strong main peaks for Co $2p_{3/2}$ and $2p_{1/2}$ with corresponding satellite structures at higher binding energies. The Co $2p_{3/2}$ main structure appeared at 781.3 eV for the $CoTiO_3$, and it was indicated at 781.1 eV with the $Co_2TiO_4$. Not only could these binding energy values be very similar to that exhibited for the 5 wt% $CoO_x/TiO_2$(fresh), but the spin-orbit splitting(${\Delta}E$) had also no noticeable difference between the cobalt titanates and a sample of the fresh catalyst. Neither of all the $CoTiO_x$ samples were active for the wet TCE oxidation, as expected, but a sample of pure $Co_3O_4$ had a good activity for this reaction. The earlier proposed model for the surface $CoO_x$ species existing with the fresh and spent catalysts is very consistent with the XPS characterization and activity measurements for the cobalt titanates.

• E2M - 전기 전자와 첨단 소재
• /
• 제7권4호
• /
• pp.317-324
• /
• 1994

In this study, new preparation method of LiCoO$_{2}$ was applied to develop cathode active material for Li rechargeable cell, and followed by X-ray diffraction analysis, electrochemical properties and initial charge/discharge characteristics as function of current density. HC8A72- and CC9A24-LiCoO$_{2}$ were prepared by heating treatment of the mixture of LiOH H$_{2}$O/CoCO$_{3}$(1:1 mole ratio) and the mixture of Li$_{2}$CO$_{3}$/CoCO$_{3}$(1:2 mole ratio) at 850 and 900.deg. C, respectively. Two prepared LiCoO$_{2}$s were identified as same structure by X-ray diffraction analysis. a and c lattice constant were 2.816.angs. and 14.046.angs., respectively. The electrochemical potential of CFM-LiCoO$_{2}$(Cyprus Foote Mineral Co.'s product), HC8A72-LiCoO$_{2}$ and CC9A24 LiCoO$_{2}$ electrode were approximately between 3.32V and 3.42V vs. Li/Li reference electrode. Stable cycling behavior was obtained during the cyclic voltammetry of LiCoO$_{2}$ electrode. According as scan rate increases, cathodic capacity decreases, but redox coulombic efficiency was about 100% at potential range between 3.6V and 4.2V vs. Li/Li reference electrode. Cathodic capacity of HC8A72-LiCoO$_{2}$ was 32% higher than that of CFM-LiCoO$_{2}$ and that of CC9A24-LiCoO$_{2}$ was 47% lower than that of CFM-LiCoO$_{2}$ at 130th cycle in the condition of lmV/sec scan rate. Constant cur-rent charge/discharge characteristics of LiCoO$_{2}$/Li cell showed increasing Ah efficiency with initial charge/discharge cycle. Specific discharge capacities of CFM and HC8A72-LiCoO$_{2}$ cathode active materials were about 93mAh/g correspondent to 34% of theretical value, 110mAh/g correspondent to 40% of theretical value, respectively. In the view of reversibility, HC8A72-LiCoO$_{2}$ was also more excellent than CFM- and CC9A24-LiCoO$_{2}$.

• Bulletin of the Korean Chemical Society
• /
• 제19권1호
• /
• pp.39-44
• /
• 1998

$LiCoO_2$ powder was synthesized in an aqueous solution by a sol-gel method and used as a cathode active material for a lithium ion rechargeable battery. The layered $LiCoO_2$ powders were prepared by igniting in air for 12 hrs at 600 ℃ $(600-LiCoO_2)$ and 850 ℃ $(850-LiCoO_2)$. The structure of the $LiCoO_2$ powder was assigned to the space group R bar 3 m (lattice parameters a=2.814 Å and c=14.04Å). The SEM pictures of $600-LiCoO_2$ revealed homogeneous and fine particles of about 1 μm in diameter. Cyclic voltammograms (CVs) of $600-LiCoO_2$ electrode displayed a set of redox peaks at 3.80/4.05 V due to the intercalation/deintercalation of the lithium ions into/out of the $LiCoO_2$ structure. CVs for the $850-LiCoO_2$ electrode had a major set of redox peaks at 3.88/4.13 V, and two small set of redox peaks at 4.18/4.42 V and 4.05/4.25 V due to phase transitions. The initial charge-discharge capacity was 156-132 mAh/g for the $600-LiCoO_2$ electrode and 158-131 mAh/g for the $850-LiCoO_2$ electrode at the current density of 0.2 mA/cm2. The cycleability of the cell consisting of the $600-LiCoO_2$ electrode was better than that of the $850-LiCoO_2$. The diffusion coefficient of the $Li^+$ ion in the $600-LiCoO_2$ electrode was calculated as $4.6{\times}10^{-8}\; cm^2/sec$.

• 한국수소및신에너지학회논문집
• /
• 제32권1호
• /
• pp.41-52
• /
• 2021

NiO and Co3O4-doped porous La(CoNi)O3 perovskite oxides were prepared from excess Ni addition by a hydrothermal method using porous silica template, and characterized as bifunctional catalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) for Zn-air rechargeable batteries in alkaline solution. Excess Ni induced to form NiO and Co3O4 in La(CoNi)O3 particles. The NiO and Co3O4-doped porous La(CoNi)O3 showed high specific surface area, up to nine times of conventionally synthesized perovskite oxide, and abundant pore volume with similar structure. Extra added Ni was partially substituted for Co as B site of ABO3 perovskite structure and formed to NiO and Co3O4 which was highly dispersed in particles. Excess Ni in La(CoNi)O3 catalysts increased OER performance (259 mA/㎠ at 2.4 V) in alkaline solution, although the activities (211 mA/㎠ at 0.5 V) for ORR were not changed with the content of excess Ni. La(CoNi)O3 with excess Ni showed very stable cyclability and low capacity fading rate (0.38 & 0.07 ㎶/hour for ORR & OER) until 300 hours (~70 cycles) but more excess content of Ni in La(CoNi)O3 gave negative effect to cyclability.

• Bulletin of the Korean Chemical Society
• /
• 제32권3호
• /
• pp.988-992
• /
• 2011

$CO_2$ adsorption on mineral sorbents has a potential to sequester $CO_2$. This study used a density functional theory (DFT) study of $CO_2$ adsorption on barium oxide (BaO) in the presence of $H_2O$ to determine the role of $H_2O$ on the $CO_2$ adsorption properties on the ($2{\times}2$; $11.05\;{\AA}{\times}11.05\;{\AA}$) BaO (100) surface because BaO shows a high reactivity for $CO_2$ adsorption and the gas mixture of power plants generally contains $CO_2$ and $H_2O$. We investigated the adsorption properties (e.g., adsorption energies and geometries) of a single $CO_2$ molecule, a single $H_2O$ molecule on the surface to achieve molecular structures and molecular reaction mechanisms. In order to evaluate the coordinative effect of $H_2O$ molecules, this study also carried out the adsorption of a pair of $H_2O$ molecules, which was strongly bounded to neighboring (-1.91 eV) oxygen sites and distant sites (-1.86 eV), and two molecules ($CO_2$ and $H_2O$), which were also firmly bounded to neighboring sites (-2.32 eV) and distant sites (-2.23 eV). The quantum mechanical calculations show that $H_2O$ molecule does not influence on the chemisorption of $CO_2$ on the BaO surface, producing a stable carbonate due to the strong interaction between the $CO_2$ molecule and the BaO surface, resulting from the high charge transfer (-0.76 e).

• 한국환경과학회지
• /
• 제14권2호
• /
• pp.221-230
• /
• 2005

Catalytic wet oxidation of trichloroethylene (TCE) in water has been conducted using $TiO_2-supported$ cobalt oxides at $36^{\circ}C$ with a weight hourly space velocity of $7,500\;h^{-1}.\;5\%\;CoO_x/TiO_2$, prepared by using an incipient wetness technique, might be the most promising catalyst for the wet oxidation although it exhibited a transient behavior in time on-stream activity. Not only could the bare support be inactive for the wet decomposition reaction, but no TCE removal also occurred by the process of adsorption on $TiO_2$ surface. The catalytic activity was independent of all particle sizes used, thereby representing no mass transfer limitation in intraparticle diffusion. XPS spectra of both fresh and used Co surfaces gave different surface spectral features for each $CoO_x,\;Co\;2P_{3/2}$ binding energy for Co species in the fresh catalyst appeared at 781.3 eV, which is very similar to the chemical states of $CoTiO_x$ such as $CO_2TiO_4\;and\;CoTiO_3$. The used catalyst exhibited a 780.3-eV main peak with a satellite structure at 795.8 eV. Based on XPS spectra of reference Co compound, the TCE-exposed Co surfaces could be assigned to be in the form of mainly $Co_3O_4$. XRD patterns for $5\%\;CoO_x/TiO_2$ catalyst indicated that the phase structure of Co species in the catalyst even before reaction is quite comparable to the diffraction lines of external $Co_3O_4$ standard. A model structure of $CoO_x$ present predominantly on titania surfaces would be $Co_3O_4$, encapsulated in thin-film $CoTiO_x$ species consisting of $Co_2TiO_4$ and $CoTiO_3$, which may be active for the decomposition of TCE in a flow of water.