• Bulletin of the Korean Chemical Society
• /
• 제18권6호
• /
• pp.612-618
• /
• 1997

$LiMn_2O_4$ powders were prepared by burning and subsequent calcination of PEG-metal nitrate precursor. After the burning stage of the precursor, some minor phases such as $Mn_2O_3$ (or $Mn_3O_4$), MnO, and carbonate were formed and single phases of $LiMn_2O_4$ were obtained by further calcinations above 400 ℃. From thermal analysis of the precursor, a violent thermal decomposition, which was indicated by a drastic weight loss accompanied by a sharp and strong exothermic peak, was observed and probably caused by an oxidation-reduction reaction between oxidizer and fuel. The formation of the minor phases could be explained in terms of the burning behavior of the precursor by employing valence concepts of propellant chemistry. The calcined powders were composed of submicron-sized but highly agglomerated particles and showed very broad particle size distribution.

• 대한전기학회:학술대회논문집
• /
• 대한전기학회 1994년도 하계학술대회 논문집 C
• /
• pp.1317-1319
• /
• 1994

The thermal properties of Cordierite$(2MgO.2Al_2O_3.5SiO_2)$ + 30 [wt%]clay + X[wt%]MnO_2$ of infrared radiator have been investigated as a function of $MnO_2$ additives (X=0, 0.1, 0.25, 0.5, 1.0, 1.5, 2.0, 2.5). The thermal expansion coefficient was decreased and the spectral emissivity was increased only in the below $4.5{\mu}m$ wavelength with increasing amaunts(wt%) of $MnO_2$ additives. Also, the infrared radiator of Cordierite system which spectral emissivity was approximately 1.0 can be attainable at from $4.5{\mu}m$ to $8{\mu}m$ wavelength. The spectral emissivity was decreased from $8{\mu}m$ to $14{\mu}m$ at X=2.5.

• 한국재료학회:학술대회논문집
• /
• 한국재료학회 2011년도 춘계학술발표대회
• /
• pp.5-5
• /
• 2011

The research and development of hybrid electric vehicle (HEV), plug-in hybrid electric vehicle (PHEV) and electric vehicle (EV) are intensified due to the energy crisis and environmental concerns. In order to meet the challenging requirements of powering HEV, PHEV and EV, the current lithium battery technology needs to be significantly improved in terms of the cost, safety, power and energy density, as well as the calendar and cycle life. One new technology being developed is the utilization of composite cathode by mixing two different types of insertion compounds [e.g., spinel $LiMn_2O_4$ and layered $LiMO_2$ (M=Ni, Co, and Mn)]. Recently, some studies on mixing two different types of cathode materials to make a composite cathode have been reported, which were aimed at reducing cost and improving self-discharge. Numata et al. reported that when stored in a sealed can together with electrolyte at $80^{\circ}C$ for 10 days, the concentrations of both HF and $Mn^{2+}$ were lower in the can containing $LiMn_2O_4$ blended with $LiNi_{0.8}Co_{0.2}O_2$ than that containing $LiMn_2O_4$ only. That reports clearly showed that this blending technique can prevent the decline in capacity caused by cycling or storage at elevated temperatures. However, not much work has been reported on the charge-discharge characteristics and related structural phase transitions for these composite cathodes. In this presentation, we will report our in situ x-ray diffraction studies on this mixed composite cathode material during charge-discharge cycling. The mixed cathodes were incorporated into in situ XRD cells with a Li foil anode, a Celgard separator, and a 1M $LiPF_6$ electrolyte in a 1 : 1 EC : DMC solvent (LP 30 from EM Industries, Inc.). For in situ XRD cell, Mylar windows were used as has been described in detail elsewhere. All of these in situ XRD spectra were collected on beam line X18A at National Synchrotron Light Source (NSLS) at Brookhaven National Laboratory using two different detectors. One is a conventional scintillation detector with data collection at 0.02 degree in two theta angle for each step. The other is a wide angle position sensitive detector (PSD). The wavelengths used were 1.1950 ${\AA}$ for the scintillation detector and 0.9999 A for the PSD. The newly installed PSD at beam line X18A of NSLS can collect XRD patterns as short as a few minutes covering $90^{\circ}$ of two theta angles simultaneously with good signal to noise ratio. It significantly reduced the data collection time for each scan, giving us a great advantage in studying the phase transition in real time. The two theta angles of all the XRD spectra presented in this paper have been recalculated and converted to corresponding angles for ${\lambda}=1.54\;{\AA}$, which is the wavelength of conventional x-ray tube source with Cu-$k{\alpha}$ radiation, for easy comparison with data in other literatures. The structural changes of the composite cathode made by mixing spinel $LiMn_2O_4$ and layered $Li-Ni_{1/3}Co_{1/3}Mn_{1/3}O_2$ in 1 : 1 wt% in both Li-half and Li-ion cells during charge/discharge are studied by in situ XRD. During the first charge up to ~5.2 V vs. $Li/Li^+$, the in situ XRD spectra for the composite cathode in the Li-half cell track the structural changes of each component. At the early stage of charge, the lithium extraction takes place in the $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ component only. When the cell voltage reaches at ~4.0 V vs. $Li/Li^+$, lithium extraction from the spinel $LiMn_2O_4$ component starts and becomes the major contributor for the cell capacity due to the higher rate capability of $LiMn_2O_4$. When the voltage passed 4.3 V, the major structural changes are from the $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ component, while the $LiMn_2O_4$ component is almost unchanged. In the Li-ion cell using a MCMB anode and a composite cathode cycled between 2.5 V and 4.2 V, the structural changes are dominated by the spinel $LiMn_2O_4$ component, with much less changes in the layered $LiNi_{1/3}Co_{1/3}Mn_{1/3}O_2$ component, comparing with the Li-half cell results. These results give us valuable information about the structural changes relating to the contributions of each individual component to the cell capacity at certain charge/discharge state, which are helpful in designing and optimizing the composite cathode using spinel- and layered-type materials for Li-ion battery research. More detailed discussion will be presented at the meeting.

• 한국대기환경학회지
• /
• 제22권3호
• /
• pp.373-381
• /
• 2006

The catalytic combustion of toluene was investigated on the Cu-Mn oxide catalysts prepared by the deposition-precipitation method. Experiment of toluene combustion was performed with a fixed bed flow reactor in the temperature range of $100{\sim}280^{\circ}C$. Among the catalysts, 1.29Cu/Mn showed the most activity at $260^{\circ}C$. The deposition-precipitation method may be showed the potential to enhance the activity of catalysts. The catalysts were characterized by BET, scanning electron microscopy (SEM), temperature-programmed reduction (TPR), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) techniques. On the basis of catalyst characterization data, the results showed that the surface of catalysts by deposition-precipitation method had uniform distribution and smaller particle size, which enhanced the reduction capability of catalysts. The XRD results showed that $Cu_{1.5}Mn_{1.5}O_{4}$ spinel phase was made by deposition-precipitation method, and increased catalyst activity and redox characteristic. It was assumed that the reduction step of $Cu_{1.5}Mn_{1.5}O_{4}$ spinel phase progressed $Cu_{1.5}Mn_{1.5}O_{4}\;to\;CuMnO_{2},\;and\;Cu_{2}O\;to\;CuMn_{2}O_{4}\;and\;Cu$.

• Bulletin of the Korean Chemical Society
• /
• 제30권3호
• /
• pp.653-656
• /
• 2009

3-Dimensionally ordered macroporous $LiMn_2O_4$ thin film was prepared by a sol-gel and dip coating method on Pt/Ti/$SiO_2$/Si substrate. An opal structure consisting of mono dispersed polystyrene beads (300 nm) was used as a template. After solution containing Mn and Li precursors was coated on the template-deposited substrate, the template and organic materials in the precursors was removed by calcination at 400 ${^{\circ}C}$. And then the 3-dimensional $LiMn_2O_4$ thin film with spinel structure was fabricated by heat treatment at 700 ${^{\circ}C}$. The structural and electrochemical property was investigated by XRD, SEM and charge-discharge cycler.

• E2M - 전기 전자와 첨단 소재
• /
• 제14권12호
• /
• pp.7-10
• /
• 2001

Orthorhombic type LiCo$_{x}$Mn$_{1-x}$ O$_2$(0$\leq$x$\leq$0.14) oxides have been synthesized by hydrothermal treatment of (Co$_{x}$Mn$_{1-x}$ )$_3$O$_4$precursors and LiOH aqueous solution at 17$0^{\circ}C$. As-synthesized powders showed well-ordered $\beta$-MaMnO$_2$structures, and the products were single crystalline particle oxides from TEM observations. The particle size decreased with increasing the amount of Co substituent. Much more improved capacity upon 100 cyclings was clearly seen in orthorhombic LiCo$_{0.1}$Mn$_{0.9}$O$_2$, comparing to orthorhombic LiMnO$_2$./TEX>.EX>.

• 청정기술
• /
• 제17권1호
• /
• pp.41-47
• /
• 2011

순수한 $MnO_2$ 산화물을 과망간산칼륨과 망간아세테이트를 사용하여 침전법으로 제조하였고 소성온도를 달리하여 CO 산화반응을 수행하였다. 촉매의 물리화학적 특성을 알아보기 위하여 XRD, $N_2$ 흡착, $H_2-TPR$, CO-TPD 등의 특성분석을 수행하였다. $MnO_2$-300 촉매는 9nm 크기 근처의 좁은 기공크기 분포로 존재하며 $181m^2/g$의 높은 비표면적을 보였다. XRD와 $H_2-TPR$ 분석으로 $MnO_2$ 촉매는 $Mn^{4+}$와 $Mn^{3+}$의 산화상태임을 확인하였다. CO-TPD 분석으로 소성온도가 높아질수록 탈착되는 $CO_2$의 양이 감소하는 것을 확인하였다. $MnO_2$ 촉매의 소성온도에 따른 최적 활성에서는 $300^{\circ}C$에서 소성한 촉매가 가장 좋은 활성을 나타냈으며, $200^{\circ}C$ 이하에서 100%의 CO 전환율을 보였다. 수분 존재하의 CO 산화반응은 활성점에 $H_2O$와 CO의 경쟁 흡착으로 촉매의 활성을 감소시켰으며 수분제거 시 활성이 건조조건과 동일하게 회복되었다.

• 한국응용과학기술학회지
• /
• 제18권3호
• /
• pp.174-179
• /
• 2001

The spinel $Fe_{3}O_{4}$ powders were synthesized using 0.2 $M-FeSO_4{\cdot}7H_{2}O$ and 0.5 M-NaOH by oxidation in air and the spinel $LiMn_{2}O_{4}$ powders were synthesized at 480 $^{\circ}C$ for 12 h in air by a sol-gel method using manganese acetate and lithium hydroxide as starting materials. The synthesized $LiMn_{2}O_{4}$ powders were mixed at portion of 5, 10, 15 and 20 wt% of $Fe_{3}O_{4}$ powders using a ball-mill. The mixed catalysts were dried at room temperature for 24 hrs. The mixed catalysts were reduced by hydrogen gas at 350 $^{\circ}C$ for 2 h. The carbon dioxide decomposition rates of the mixed catalysts were 90% in all the mixed catalysts but the decomposition rate of carbon dioxide was increased with adding $LiMn_{2}O_{4}$ powders to $Fe_{3}O_{4}$ powders.

• Korean Chemical Engineering Research
• /
• 제49권5호
• /
• pp.633-638
• /
• 2011

Mn이 치환된 헥사알루미네이트 촉매인 $LaMnAl_{11}O_{19}$, $BaMnAl_{11}O_{19}$, $SrMnAl_{11}O_{19}$을 $(NH_4)_2CO_3$ 공침법을 이용하여, $1,200^{\circ}C$ 5시간 소성을 통해 제조하였다. X-선 회절, 질소흡착을 통해 촉매의 결정구조와 비표면적을 분석한 결과, 결정 격자 내 거울면에 La이 존재하는 $LaMnAl_{11}O_{19}$이 $BaMnAl_{11}O_{19}$과 $SrMnAl_{11}O_{19}$보다 우수한 헥사알루미네이트 결정 구조를 가지는 동시에 13 $m^2/g$의 높은 비표면적을 가지고 있었다. 또한 SEM 분석을 통해 $LaMnAl_{11}O_{19}$이 특유의 판상구조가 잘 발달함을 확인하였다. 메탄 연소 활성은 다음과 같은 차례로 증가하였고: $LaMnAl_{11}O_{19}$ > $SrMnAl_{11}O_{19}$ > $BaMnAl_{11}O_{19}$. 메탄 연소 활성은 비표면적에 의존하였다. $LaMnAl_{11}O_{19}$에 60 wt%의 $CeO_2$를 첨가하고 $700^{\circ}C$의 저온에서 소성한 경우 $700^{\circ}C$의 저온에서 100% 전환율에 도달함으로써 ceria 첨가에 의한 메탄 연소 개선 효과를 확인할 수 있었으며, 이 촉매가 저온 및 중온 영역의 메탄 연소 촉매로 활용될 수 있음을 확인하였다. 그러나, 이 촉매의 경우 $1,200^{\circ}C$의 고온에서 5시간 소성한 후에는 ceria입자 크기의 증가로 인해 메탄의 연소 활성 개선 효과를 잃게됨으로 고온용 연소 촉매로서의 사용은 한계가 있음을 확인하였다.

• Korean Chemical Engineering Research
• /
• 제51권4호
• /
• pp.460-464
• /
• 2013

본 연구에서는 $LiMn_2O_4$ 제조에서 Mn 원료로 사용되는 CMD를 seed 첨가법을 사용하여 제조하고자 하였으며, Seed의 열처리 온도가 CMD 합성에 미치는 영향을 고찰하고, 그로부터 제조되는 $LiMn_2O_4$의 전기화학적 특성을 평가하고자 하였다. 제조한 시료의 물성평가는 X-선 회절 분석법(XRD), 주사전자현미경(SEM)을 통하여 실시하였다. 그 결과, $MnCO_3$를 $300^{\circ}C$ 이상의 온도에서 열처리하여 seed로 사용할 경우 ${\gamma}-MnO_2$ 상의 CMD가 얻어졌으며, 그 CMD를 LMO 제조에 사용할 경우 전기화학적 특성이 비교적 우수한 LMO가 얻어졌다.