• Bulletin of the Korean Chemical Society
• /
• 제14권1호
• /
• pp.137-143
• /
• 1993

The tetranuclear heterometallic complex CpMo$Os_3(CO)_{10}({\mu]-H)2[{\mu}3-{\eta}^2-C(O)CH_2Tol]\;(1,\;Cp={\eta}^5-C_5H_5,\;Tol=p-C_6H_4Me)$ has been examined by variable-temperature $^{13}$C-NMR spectroscopy and by a full three-dimensional X-ray structual analysis. Complex 1 crystallizes in the orthorhombic space group Pna2$_1$ with a = 12.960(1) ${\AA}$, b = 11.255(l) ${\AA}$, c = 38.569(10)${\AA}$, V = 5626(2) ${\AA}^3$ and ${\rho}$(calcd) = 2.71 gcm$^{-3}$ for Z = 8 and molecular weight 1146.9. Diffraction data were collectedon a CAD4 diffractometer, and the structure was refined to $R_F$ = 9.7% and $R_{W^F}$ = 9.9% for 2530 data (MoK${\alpha}$ radiation). There are two essentially equivalent molecules in the crystallographic asymmetric unit. The tetranuclear molecule contains a triangulated rhomboidal arrangement of metal atoms with Os(2) and Mo at the two bridgehead positions. The metal framework is planar; the dihedral angle between Os(l)-Os(2)-Mo and Os(3)-Os(2)-Mo planes is 180$^{\circ}$. A triply bridging (${\mu}_3,\;{\eta}^2$) acyl ligand lies above the Os(l)-Os(2)-Mo plane; the oxygen atom spans the two bridgehead positions, while the carbon atom spans one bridgehead position and an acute apical position. The molecular architecture is completed by an ${\eta}^5$-cyclopentadienyl ligand and a semi-triply bridging carbonyl ligand on the molybdenum atom, and nine terminal carbonyl ligands-four on Os(3), three on Os(l), and two on Os(2). The two hydride ligands are inferred to occupy the Os(l)-Os(2) and Mo-Os(3) edges from structural and NMR data.

• 한국수소및신에너지학회논문집
• /
• 제28권1호
• /
• pp.9-16
• /
• 2017

Hydrogen forms metal hydrides with some metals and alloys leading to solid-state storage under moderate temperature and pressure that gives them the safety advantage over the gas and liquid storage methods. However, it has disadvantages of slow hydrogen adsorption-desorption time and low thermal conductivity. To improve characteristics of metal hydrides, it is important that activation and thermal conductivity of metal hydrides are improved. In this study, we have been investigated hydrogen storage properties of Hydralloy C among Ti-Mn alloys. Also, the characteristics of activation and thermal conductivity of Hydralloy C were enhanced to improve kinetics of hydrogen adsorption-desorption. As physical activation method, PHEM (planetary high energy mill) was performed in Ar or $H_2$ atmosphere. Hydralloy C was also activated by $TiCl_3$ catalyst. To improve thermal conductivity, various types of ENG (expanded natural graphite) were used. The prepared samples were compacted at pressure of 500 bar. As a result, the activation properties of $H_2$ PHEM treated Hydralloy C was better than the other activation methods. Also, the amounts of hydrogen storage showed up to 1.6 wt%. When flake type ENG was added to Hydralloy C, thermal conductivity and hydrogen storage properties were improved.

• 한국분말재료학회지
• /
• 제13권5호
• /
• pp.327-335
• /
• 2006

In the development of new hydrogen absorbing materials for a next generation of metal hydride electrodes for rechargeable batteries, metastable Mg-Ni-based compounds find currently special attention. Amor phous-nanocrystalline $Mg_{63}Ni_{30}Y_7$ and $Mg_{50}Ni_{30}Y_{20}$ alloys were produced by mechanical alloying and melt-spinning and characterized by means of XRD, TEM and DSC. On basis of mechanically alloyed Mg-Ni-Y powders, complex hydride electrodes were fabricated and their electrochemical behaviour in 6M KOH (pH=14,8) was investigated. The electrodes made from $Mg_{63}Ni_{30}Y_7$ powders, which were prepared under use of a SPEX shaker mill, with a major fraction of nanocrystalline phase reveal a higher electrochemical activity far hydrogen reduction and a higher maximum discharge capacity (247 mAh/g) than the electrodes from alloy powder with predominantly amorphous microstructure (216 mAh/g) obtained when using a Retsch planetary ball mill at low temperatures. Those discharge capacities are higher that those fur nanocrystalline $Mg_2Ni$ electrodes. However, the cyclic stability of those alloy powder electrodes was low. Therefore, fundamental stability studies were performed on $Mg_{63}Ni_{30}Y_7$ and $Mg_{50}Ni_{30}Y_{20}$ ribbon samples in the as-quenched state and after cathodic hydrogen charging by means of anodic and cathodic polarisation measurements. Gradual oxidation and dissolution of nickel governs the anodic behaviour before a passive state is attained. A stabilizing effect of higher fractions of yttrium in the alloy on the passivation was detected. During the cathodic hydrogen charging process the alloys exhibit a change in the surface state chemistry, i.e. an enrichment of nickel-species, causing preferential oxidation and dissolution during subsequent anodization. The effect of chemical pre-treatments in 1% HF and in $10\;mg/l\;YCl_3/1%\;H_2O_2$ solution on the surface degradation processes was investigated. A HF treatment can improve their anodic passivation behavior by inhibiting a preferential nickel oxidation-dissolution at low polarisation, whereas a $YCl_3/H_2O_2$ treatment has the opposite effect. Both pre-treatment methods lead to an enhancement of cathodically induced surface degradation processes.

• 공업화학
• /
• 제8권4호
• /
• pp.568-574
• /
• 1997

Ni/MH전지에서 Cu 도금이 MH(metal hydride)음극의 전극 특성에 미치는 영향을 실험적으로 조사하였다. $LaNi_5$와 Cu도금된 $LaNi_5$를 활물질로 사용하여 냉간압착법과 페이스트법의 혼용법으로 전극을 제조하였다. 그 결과 소량의 CMC(carboxymethylcellulose sodium salt)를 첨가하고 열처리를 행하지 않은 전극이 높은 방전용량을 보였다. $LaNi_5$보다는 Cu 도금된 $LaNi_5$를 활물질로 사용하여 제조한 전극의 방전용량이 증가하였으며, 이는 $LaNi_5$표면에 도금된 구리에 의해 전극의 전자 전도도가 증가되었기 때문이며 도금된 구리의 양이 증가할 수록 그 효과는 현저하였다. 또한 전극의 방전용량은 산성 무전해도금의 경우가 알칼리성 무전해도금을 행한 전극보다 우수한 용량을 나타내었다. Al이 첨가된 $LaNi_{4.5}Al_{0.5}$ 전극이 $LaNi_5$전극보다 우수한 방전용량을 보였다. 구리 도금이 $LaNi_5$의 피독특성에 미치는 영향을 CO기체의 피독실험으로 조사하였다.

• 한국결정성장학회지
• /
• 제20권1호
• /
• pp.1-6
• /
• 2010

혼합소스 hydride vapor phase epitaxy(HVPE) 방법으로 CuInGaSe(CIGS) 혼합 소스를 형성하였다. 각 금속들은 일정 비율로 혼합하였고, $1090^{\circ}C$에서 1시간 30분간 soaking 하였다. 혼합된 소스를 분말형태로 만든 후, 직경 10 mm 크기의 pellet을 만들었다. 시료는 혼합소스 HVPE 에서 소성 한 후 e-beam 으로 Mo이 증착된 기판 위에 증착하였다. Scanning electron microscope(SEM), Energy dispersive X-ray spectrum(EDS) 그리고 X-ray diffraction(XRD) 측정을 통하여 그 특성을 분석하였으며 박막의 특성은 (112), (204)/(220), (116)/(312)그리고 (400) 방향 등의 다결정 특성을 나타내었다.

• 한국수소및신에너지학회논문집
• /
• 제16권1호
• /
• pp.92-101
• /
• 2005

[ $Li_3AlH_6$ ] (5.6wt% theoretical hydrogen storage capacity) powders with and without Ti-containing dopants have been successfully synthesized by mechanochemical reaction near room temperatures from mixtures of LiH and $LiAlH_4$ powders. It has been observed that single phase $Li_3AlH_6$ could be obtained within 2-3 hours of milling, but the addition of reactive $TiCl_2\;or\;TiCl_3$ to the starting mixtures. caused partial decomposition of $LiAlH_4$ into LiCl and free Al with gaseous $H_2$. By addition of these reactive dopants to the as-synthesized $Li_3AlH_6$, this problem could be solved. The addition of 2 mol% $TiCl_2\;or\;TiCl_3\;to\;Li_3AlH_6$ decreased the decomposition start temperature up to 30-50$^{\circ}C$, while that of Ti or $TiH_2$ did not change the thermal decomposition behavior of $Li_3AIH_6$.

• 한국수소및신에너지학회논문집
• /
• 제22권3호
• /
• pp.380-385
• /
• 2011

$MgH_2$ was synthesized by hydriding chemical vapor deposition (HCVD). In this study, we examined the hydrogen storage property of $MgH_2$ synthesized by HCVD. The results of pressure-composition-temperature (PCT) measurement showed that the HCVDed $MgH_2$ reversibly absorbed hydrogen as much as 6 wt%. Each hydrogenation rate was very greater than the conventional alloy methods. The reason was that the particle size made by HCVD was small as approximately 1 ${\mu}m$. The PCT of $MgH_2$ made by HCVD methode was similar to a commercial $MgH_2$. The ${\Delta}H$ and ${\Delta}S$ value are respectively -76.8 $kJ/mol{\cdot}H_2$ and -137.4 $kJ/mol{\cdot}H_2$. Mg made by HCVD methode was activated easily than commercial Mg. Also the initial reaction rate was faster than that of commercial $MgH_2$. 70% of the total storage were stored during 400s.

• 자원리싸이클링
• /
• 제28권6호
• /
• pp.18-25
• /
• 2019

폐니켈수소전지에 함유되어 있는 세륨을 회수하기 위하여 침출 및 침전을 통해 회수한 희토류복합 침전분말을 수산화나트륨(NaOH) 수용액에 반응온도 70 ℃ 및 반응시간 4시간의 조건에서 이온치환반응을 통하여 희토류 수산화물로 변환시켰다. 이후 희토류 수산화물은 반응온도 80 ℃에서 반응시간 4시간의 조건에서 공기를 주입하며 산화반응을 통해 세륨을 Ce³⁺에서 Ce⁴⁺로 전환시켰다. 세륨의 산화율은 XPS 분석을 통해 약 25 %로 확인하였으며, 산화반응이 완료된 분말은 묽은 황산에 대한 용해도 차이를 이용하여 세륨과 나머지 희토류를 분리하였다. 최종적으로 회수된 분말은 XRD 분석을 통해 수산화세륨(Ce(OH)₄)의 결정상을 확인하였으며, 이때 세륨의 순도는 약 94.6 %, 회수율은 97.3 %를 나타내었다.

• 한국분말재료학회지
• /
• 제25권3호
• /
• pp.213-219
• /
• 2018

We report a method for preparing rare earth oxides ($Re_xO_y$) from the recycling process for spent Ni-metal hydride (Ni-MH) batteries. This process first involves a leaching of spent Ni-MH powders with sulfuric acid at $90^{\circ}C$, resulting in rare earth precipitates (i.e., $NaRE(SO_4)_2{\cdot}H_2O$, RE = La, Ce, Nd), which are converted into rare earth oxides via two different approaches: i) simple heat treatment in air, and ii) metathesis reaction with NaOH at $70^{\circ}C$. Not only the morphological features but also the crystallographic structures of all products are systematically investigated using field-emission scanning electron microscopy (FESEM) and X-ray diffraction (XRD); their thermal behaviors are also analyzed. In particular, XRD results show that some of the rare earth precipitates are converted into oxide form (such as $La_2O_3$, $Ce_2O_3$, and $Nd_2O_3$) with heat treatment at $1200^{\circ}C$; however, secondary peaks are also observed. On the other hand, rare earth oxides, RExOy can be successfully obtained after metathesis of rare earth precipitates, followed by heat treatment at $1000^{\circ}C$ in air, along with a change of crystallographic structures, i.e., $NaRE(SO_4)_2{\cdot}H_2O{\rightarrow}RE(OH)_3{\rightarrow}RE_xO_y$.

• 한국수소및신에너지학회논문집
• /
• 제28권2호
• /
• pp.156-165
• /
• 2017

This study quantitatively assessed the environmental impacts of fuel cell (FC) systems by performing life cycle assessment (LCA) and analyzed their energy efficiencies based on energy return on investment (EROI) and electrical energy stored on investment (ESOI). Molten carbonate fuel cell (MCFC) system and polymer electrolyte membrane fuel cell (PEMFC) system were selected as the fuel cell systems. Five different paths to produce hydrogen ($H_2$) as fuel such as natural gas steam reforming (NGSR), centralized naptha SR (NSR(C)), NSR station (NSR(S)), liquified petroleum gas SR (LPGSR), water electrolysis (WE) were each applied to the FCs. The environmental impacts and the energy efficiencies of the FCs were compared with rechargeable batteries such as $LiFePO_4$ (LFP) and Nickel-metal hydride (Ni-MH). The LCA results show that MCFC_NSR(C) and PEMFC_NSR(C) have the lowest global warming potential (GWP) with 6.23E-02 kg $CO_2$ eq./MJ electricity and 6.84E-02 kg $CO_2$ eq./MJ electricity, respectively. For the impact category of abiotic resource depletion potential (ADP), MCFC_NGSR(S) and PEMFC_NGSR(S) show the lowest impacts of 7.42E-01 g Sb eq./MJ electricity and 7.19E-01 g Sb eq./MJ electricity, respectively. And, the energy efficiencies of the FCs are higher than those of the rechargeable batteries except for the case of hydrogen produced by WE.