• Title/Summary/Keyword: ${\delta}-MnO_2$

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Electrical Characteristics of Cathode Li($Mn_{1-\delta}$$M_{\delta}$)$_2$$O_4$ Substituted by Transition Metals in Li-Ion Secondary Batteries (전이금속 치환 리튬이온 이차전지 정극 Li($Mn_{1-\delta}$$M_{\delta}$)$_2$$O_4$의 전기적 특성)

  • 박재홍;김정식;유광수
    • Journal of the Korean Ceramic Society
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    • v.37 no.5
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    • pp.466-472
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    • 2000
  • As cathode materials of LiMn2O4-based lithium-ion secondary batteries, Li(Mn1-$\delta$M$\delta$)2O4 (M=Ni and Co, $\delta$=0, 0.05, 0.1 and 0.2) materials which Co and Ni are substituted for Mn, were syntehsized by the solid state reaction at 80$0^{\circ}C$ for 48 hours. No second phases were formed in Li(Mn1-$\delta$M$\delta$)2O4 system with substitution of Co. However, substitution of Ni caued to form a second phase of NiO when its composition exceeded over 0.2 of $\delta$ in Li(Mn1-$\delta$M$\delta$)2O4. As the results of charging-discharging test, the maximum capacity of Li(Mn1-$\delta$M$\delta$)2O4 appeared in $\delta$=0.1 for both Co and Ni. Also, Li(Mn1-$\delta$M$\delta$)2O4 electrode showed higher capacity and better cycle performance than LiMn2O4.

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Electrical Characteristics of Li(Mn$_{1-}$$\delta$Nb$\delta$)$_2$O$_4$ Cathode Materials for Li-Ion Secondary Batteries (리튬 이온 이차전지 Cathode용 Li(Mn$_{1-}$$\delta$Nb$\delta$)$_2$O$_4$의 전기적 특성)

  • 오용주;유광수
    • Journal of the Korean Ceramic Society
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    • v.35 no.9
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    • pp.995-1001
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    • 1998
  • As a basic study for cathode materials of {{{{ { {LiMn }_{2 }O }_{4 } }}-based lithium-ion secondary batteries Li({{{{ { { { {Mn }_{1-$\delta$ }Nb }_{$\delta$} )}_{2 }O }_{4 } }} ($\delta$=0.05, 0.1, 0.2) materials which Nb is substituted for Mn were synthesized by the solid state reaction at 80$0^{\circ}C$ and 110$0^{\circ}C$ respectively. The second phase {{{{ { LiNbO}_{3 } }} appeared above $\delta$=0.1 As the result of im-pedance analysis as the amount of substituted Nb increased the resistivity of grain boundary increased greatly. Compared to undoped-{{{{ { {LiMn }_{2 }O }_{4 } }} the electrical conductivity of Li({{{{ { { { {Mn }_{1-$\delta$ }Nb }_{$\delta$} )}_{2 }O }_{4 } }} decreased slightly but is charging capacity and potential plateau increased.

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Cathodic Polarization of $La_{0.5}Sr_{0.5}MnO_{3-\delta}$ on $Ce_{0.8}Gd_{0.2}O_{1.9}$ Electrolyte ($Ce_{0.8}Gd_{0.2}O_{1.9}$ 전해질에서 $La_{0.5}Sr_{0.5}MnO_{3-\delta}$ 양극의 과전압특성)

  • 윤희성;노의범;김병호
    • Journal of the Korean Ceramic Society
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    • v.35 no.9
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    • pp.981-987
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    • 1998
  • $La_{0.5}Sr_{0.5}MnO_{3-\delta}$ as air electrode for soild oxide fuel cell was synthesized by a citrate process and its cathodic polarization was determinated by the current interruption method on the Gd-doped ceria as electrolyte. The addition of citric acid increased the exothermic heat for the formation of $La_{0.5}Sr_{0.5}MnO_{3-\delta}$ perovskite oxide. The degree of the initial particle agglomeration was affected by the exothermic heat. Also the increase of cal-cination temperature enlarged the particle size and the higher sintering temperature accelerated the den-sification of $La_{0.5}Sr_{0.5}MnO_{3-\delta}$ layer after its being painted on $Ce_{0.8}Gd_{0.2}O_{1.9}$ electrolyte. In this study $La_{0.5}Sr_{0.5}MnO_{3-\delta}$ synthesized by citrate process of which the molar ratio of citric acid to metal nitrate was 2 calcined at $650^{\circ}C$ for 2hr and sintered at 1100 at $1200^{\circ}C$ for 4 hrs after slurry coating on Ce0.8Gd0.2O1.9 electrlyte showed the lowest cathodic polarization.

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The Study of Analytical Chemistry of the Modification of Manganese Dioxide (Report one). The Study of ${\alpha},{\beta},{\gamma}\;and\;{\delta}-MnO_2$ by Differential Heating Curves (變態二酸化망간의 分析化學的 硏究 (第一報). ${\alpha},{\beta},{\gamma}$${\delta}-MnO_2$ 의 示差熱曲線에 對한 考察)

  • Chan Ho Kim
    • Journal of the Korean Chemical Society
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    • v.15 no.5
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    • pp.236-241
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    • 1971
  • Various modifications of manganese dioxide have been discussed in terms of the chemical analysis by differential heating curve. The transformation temperatures of the modifications were observed as follows; ${\alpha}-\;and\;{\beta}-MnO_2$ are both $580^{\circ}C∼650^{\circ}C$, ${\gamma}-MnO_2$is is $405^{\circ}C~605^{\circ}C$ and ${\delta}-MnO_2$is $860^{\circ}C~875^{\circ}C$, respectively. Endothermic peaks appeared at the transformation temperatures mentioned above. The restoration temperatures of transformation is completed depending on the amounts of the given samples, but the temperatures of the top of endothermic peaks are nearly constant. The curves of ${\alpha}-,{\beta}-MnO_2$and ${\delta}-MnO_2$ show small peaks while that of ${\gamma}-MnO_2$ shows a sharp and broad peak.

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Charge-discharge Properties by Cut-off Voltage Changes of Li(${Mn_{1-\delta}}{M_{\delta}$)$_2$$O_4$ and ${LiMn_2}{O_4}$in Li-ion Secondary Batteries (코발트와 니켈로 치환한 리튬이온 이차전지 Cathode, Li(${Mn_{1-\delta}}{M_{\delta}$)$_2$$O_4$${LiMn_2}{O_4}$의 Cut-off 전압 변화에 따른 충방전 특성)

  • 유광수;박재홍;이승원;조병원
    • Journal of the Korean Ceramic Society
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    • v.38 no.5
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    • pp.424-430
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    • 2001
  • Cut-off 전압 변화에 따른 충방전 특성을 알아보기 위하여 Mn을 다른 전이 금속이 Co와 Ni로 소량 치환시킨 Li(M $n_{1-{\delta}}$ $n_{\delta}$)$_2$ $O_4$(M=Ni, Co, $\delta$=0, 0.05, 0.1, 0.2)를 고상 반응법으로 80$0^{\circ}C$에서 48시간 동안 유지하여 합성하였다. 충방전의 cut-off 전압은 2.5~4.4V, 3.0~4.5V, 3.5~4.5V, 3.5V~4.7V의 네 가지 전압범위고 하였다. 충방전 실험결과, Li(M $n_{1-{\delta}}$ $n_{\delta}$)$_2$ $O_4$의 용량은 각각 Co와 Ni의 $\delta$=0.1에서 최대를 보였다. Co 치환 조성 재료와 순물질 모두에서 최대의 용량을 보인 cut-off 전압대는 3.5~4.5V 이었는데 이때의 Li(M $n_{0.9}$ $Co_{0.1}$)$_2$ $O_4$와 LiM $n_2$ $O_4$의 초기 충전용량과 초기 방전용량은 각각 118, 119mAh/g과 114, 104mAh/g 이었다. 또한 모든 cut-off 전압대에서 Li(M $n_{0.9}$ $Co_{0.1}$)$_2$ $O_4$는 순수한 LiM $n_2$ $O_4$보다 더 높은 용량과 우수한 싸이클 성능을 보였으며 그 결과는 밀착형 전지구성에서도 일치하였다.하였다.

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CO2 Decomposition Characteristics of Activated(Fe1-xMnx)3O4-δ and (Fe1-xCox)3O4-δ (활성화된(Fe1-xMnx)3O4-δ과 (Fe1-xCox)3O4-δ의 이산화탄소 분해 특성)

  • Park, Won-Shik;Oh, Kyoung-Hwan;Rhee, Sang-In;Suhr, Dong-Soo
    • Korean Journal of Materials Research
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    • v.23 no.4
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    • pp.219-226
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    • 2013
  • Activated magnetite ($Fe_3O_{4-{\delta}}$) has the capability of decomposing $CO_2$ proportional to the ${\delta}$-value at comparatively low temperature of $300^{\circ}C$. To enhance the $CO_2$ decomposition capability of $Fe_3O_{4-{\delta}}$, $(Fe_{1-x}Co_x)_3O_{4-{\delta}}$ and $(Fe_{1-x}Mn_x)_3O_{4-{\delta}}$ were synthesized and then reacted with $CO_2$. $Fe_{1-x}Co_xC_2O_4{\cdot}2H_2O$ powders having Fe to Co mixing ratios of 9:1, 8:2, 7:3, 6:4, and 5:5 were synthesized by co-precipitation of $FeSO_4{\cdot}7H_2O$ and $CoSO_4{\cdot}7H_2O$ solutions with a $(NH_4)_2C_2O_4{\cdot}H_2O$ solution. The same method was used to synthesize $Fe_{1-x}Mn_xC_2O_4{\cdot}2H_2O$ powders having Fe to Mn mixing ratios of 9:1, 8:2, 7:3, 6:4, 5:5 with a $MnSO_4{\cdot}4H_2O$ solution. The thermal decomposition of synthesized $Fe_{1-x}Co_xC_2O_4{\cdot}2H_2O$ and $Fe_{1-x}Mn_xC_2O_4{\cdot}2H_2O$ was analyzed in an Ar atmosphere with TG/DTA. The synthesized powders were heat-treated for 3 hours in an Ar atmosphere at $450^{\circ}C$ to produce activated powders of $(Fe_{1-x}Co_x)_3O_{4-{\delta}}$ and $(Fe_{1-x}Mn_x)_3O_{4-{\delta}}$. The activated powders were reacted with a mixed gas (Ar : 85 %, $CO_2$ : 15 %) at $300^{\circ}C$ for 12 hours. The exhaust gas was analyzed for $CO_2$ with a $CO_2$ gas analyzer. The decomposition of $CO_2$ was estimated by measuring $CO_2$ content in the exhaust gas after the reaction with $CO_2$. For $(Fe_{1-x}Mn_x)_3O_{4-{\delta}}$, the amount of $Mn^{2+}$ oxidized to $Mn^{3+}$ increased as x increased. The ${\delta}$ value and $CO_2$ decomposition efficiency decreased as x increased. When the ${\delta}$ value was below 0.641, $CO_2$ was not decomposed. For $(Fe_{1-x}Co_x)_3O_{4-{\delta}}$, the ${\delta}$ value and $CO_2$ decomposition efficiency increased as x increased. At a ${\delta}$ value of 0.857, an active state was maintained even after 12 hours of reaction and the amount of decomposed $CO_2$ was $52.844cm^3$ per 1 g of $(Fe_{0.5}Co_{0.5})_3O_{4-{\delta}}$.

Phase Transitions of $LiMn_2O_4$ on $CO_2$ Decomposition (($CO_2$ 분해시 $LiMn_2O_4$의 상변화)

  • Kwoen, Tae-Hwan;Yang, Chun-Mo;Park, Young-Goo;Cho, Young-Koo;Rim, Byung-O
    • Journal of the Korean Applied Science and Technology
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    • v.20 no.1
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    • pp.33-43
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    • 2003
  • $LiMn_2O_4$ catalyst for $CO_2$ decomposition was synthesized by oxidation method for 30 min at 600$^{\circ}C$ in an electric furnace under air condition using manganese(II) nitrate $(Mn(NO_3)_2{\cdot}6H_2O)$, Lithium nitrate ($LiNO_3$) and Urea $(CO(NH_2)_2)$. The synthesized catalyst was reduced by $H_2$ at various temperatures for 3 hr. The reduction degree of the reduced catalysts were measured using the TGA. And then $CO_2$ decomposition rate was measured using the reduced catalysts. Phase-transitions of the catalysts were observed after $CO_2$ decomposition reaction at an optimal decomposition temperature. As the result of X-ray powder diffraction analysis, the synthesized catalyst was confirmed that the catalyst has the spinel structure, and also confirmed that when it was reduced by $H_2$, the phase of $LiMn_2O_4$ catalyst was transformed into $Li_2MnO_3$ and $Li_{1-2{\delta}}Mn_{2-{\delta}}O_{4-3{\delta}-{\delta}'}$ of tetragonal spinel phase. After $CO_2$ decomposition reaction, it was confirmed that the peak of $LiMn_2O_4$ of spinel phase. The optimal reduction temperature of the catalyst with $H_2$ was confirmed to be 450$^{\circ}C$(maximum weight-increasing ratio 9.47%) in the case of $LiMn_2O_4$ through the TGA analysis. Decomposition rate(%) using the $LiMn_2O_4$ catalyst showed the 67%. The crystal structure of the synthesized $LiMn_2O_4$ observed with a scanning electron microscope(SEM) shows cubic form. After reduction, $LiMn_2O_4$ catalyst became condensed each other to form interface. It was confirmed that after $CO_2$ decomposition, crystal structure of $LiMn_2O_4$ catalyst showed that its particle grew up more than that of reduction. Phase-transition by reduction and $CO_2$ decomposition ; $Li_2MnO_3$ and $Li_{1-2{\delta}}Mn_{2-{\delta}}O_{4-3{\delta}-{\delta}'}$ of tetragonal spinel phase at the first time of $CO_2$ decomposition appear like the same as the above contents. Phase-transition at $2{\sim}5$ time ; $Li_2MnO_3$ and $Li_{1-2{\delta}}Mn_{2-{\delta}}O_{4-3{\delta}-{\delta}'}$ of tetragonal spinel phase by reduction and $LiMn_2O_4$ of spinel phase after $CO_2$ decomposition appear like the same as the first time case. The result of the TGA analysis by catalyst reduction ; The first time, weight of reduced catalyst increased by 9.47%, for 2${\sim}$5 times, weight of reduced catalyst increased by average 2.3% But, in any time, there is little difference in the decomposition ratio of $CO_2$. That is to say, at the first time, it showed 67% in $CO_2$ decomposition rate and after 5 times reaction of $CO_2$ decomposition, it showed 67% nearly the same as the first time.

The Study of Analytical Chemistry of the Modification of Manganese Dioxide (III). Quntitative Determination of Pyrolusite by Differential Heating Curves (변태 이산화망간의 분석 화학적 연구 (제3보) 시차 열곡선에 의한 Pyrolusite의 정량)

  • Kim Chan-Ho
    • Journal of the Korean Chemical Society
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    • v.17 no.2
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    • pp.122-125
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    • 1973
  • A study on the endothermic peak of transformation of the pyrolusite was made by using differential thermal curves for analytical reproducibility, and it was done in quantity on range from 50 mg to 450 mg of pyrolusite species. The separation of ${\alpha}-MnO_2$ peak was impossible due to the overlapping between $\alpha$ and pyrolusite peaks, and the pyrolusite was determined among the species, ${\gamma}-MnO_2$ and ${\delta}-MnO_2$, with an error ranging from $5{\%}$ to $10{\%}$.

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Cell Properties for SOFC Using Synthesized Powder of Electrolyte LSGM System and Cathode LSM System (LSGM 전해질과 LSM 양극의 합성분말을 이용한 SOFC 단위전지의 특성)

  • Lee, Mi-Jai;Nam, Jeong-Hee;Choi, Byung-Hyun
    • Journal of the Korean Ceramic Society
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    • v.39 no.4
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    • pp.359-366
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    • 2002
  • The purpose of this study is to investigate the properties of LSGM electrolyte and LSM cathode. The unit cell based on the optimum conditions and processing for high performance was fabricated and measured. The single phase of $LaGaO_3$ was obtained on sintering at $1500^{\circ}$ for 6h with composition of $(La_{0.85}Sr_{0.15})(Ga_{0.8}Mg_{0.2})O_{3-\delta}와 (La_{0.8}Sr_{0.2})(Ga_{0.8}Mg_{0.2})O_{3-\delta}$ and $(La_{0.85}Sr_{0.15})(Ga_{0.8}Mg_{0.2})O_{3-\delta}$. The grain size of the sintered body was about $10∼30{\mu}m$ and electrical conductivity was 0.13 S/cm measured at $800^{\circ}$. The single phase of $LaMnO_3$ structure in $(La1-xSrx)MnO_3$ system was obtained at x=0∼0.2 and the particle size of the synthesized powder was about 40 nm. The unit cell was prepared by firing at $1200^{\circ}$ for 1h with $(La_{0.9}Sr_{0.1})MnO_3$ cathode and 0.9NiO-0.1YSZ anode screen-printed on surfaces of $(La_{0.8}Sr_{0.2})(Ga_{0.8}Mg_{0.2})O_{3-\delta}$ electrolyte. The grain size of the electrode was close to $1{\mu}m$ and the electrode had porous structure. The maximum power density of unit cell showed $0.3W/cm^2$ at $800^{\circ}$.