• 공업화학
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• 제10권6호
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• pp.832-837
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• 1999

수용액계에서 정극활물질의 안정성을 1 M LiOH 용액에서 Tafel plot를 통해서 측정하였으며, 이 때 $LiM_xMn_{2-x}O_4$(x=0.05~0.1) 전극은 100 mA에서 0.13~0.15 mV의 과전압으로 $LiMn_2O_4$ 전극보다 0.05 mV가 낮은 과전압을 나타냈다. 또한 전위변화에 따른 전해질의 전도도는 $LiM_xMn_{2-x}O_4$가 스피넬 구조의 $LiMn_2O_4$보다 높고 나타났으며, $Mn^{+2}$의 용해에 의한 용액저항은 상대적으로 낮게 나타났다.

• 한국세라믹학회지
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• 제37권5호
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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.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2000년도 춘계학술대회 논문집 전자세라믹스 센서 및 박막재료 반도체재료 일렉트렛트 및 응용기술
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• pp.117-120
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• 2000

The relation of crystal phase and charge/discharge capacity of $Li[Li_yMn_{2-y}]O_4$ were studied for different degrees of Li substitution (y). All cathode material showed spinel phase based on cubic phase in X-ray diffraction. Other peaks didn't show in spite of the increase of y value in $Li[Li_yMn_{2-y}]O_4$. Ununiform of $Li[Li_yMn_{2-y}]O_4$ which calcinated by (111) face and (222) face was more stable than that of pure $LiMn_2O_4$. In addition, At TG analysis, calcined $Li[Li_{0.1}Mn_{1.9}]O_4$ exhibited much mass loss at $800{\mu}m$. The cycle performance of the $Li(Li_yMn_{2-y}]O_4$ was improved by the substitution of $Li^{1+}$ for $Mn^{3+}$ in the octahedral sites. Specially, $Li[Li_{0.08}Mn_{1.92}]O_4$ and $Li[Li_{0.1}Mn_{1.9}]O_4$ cathode materials showed the charge and discharge capacity of about 125mAh/g at first cycle, and about 95mAh/g after 70th cycle. It is excellent than that of pure $LiMn_2O_4$, which 125mAh/g at first cycle, 65mAh/g at 70th.

• 공업화학
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• 제9권2호
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• pp.220-225
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• 1998

스피넬 구조의 $LiMn_2O_4$를 $Li_2CO_3$와 $MnO_2$를 사용하여 $750{\sim}900^{\circ}C$에서 소성해서 합성하였다. 이 때 $850^{\circ}C$에서 12시간 동안 소성할 경우 입방정 구조의 $LiMn_2O_4$가 얻어졌다. 그러나 $900^{\circ}C$에서 소성해서 합성할 경우 산소의 발생으로 인해서 0.06M의 $Mn^{+4}$가 $Mn^{+3}$로 전이되면서 $LiMn_2O_{3.97}$이 얻어졌다. 이것은 스피넬 구조의 $LiMn_2O_4$에서 octahedral site의 $Mn^{+3}$ 이온의 증가로 인해서 Jahn-Teller distortion이 발생되며, 이로 인해 $3.6{\sim}4.3V_{Li/Li}+$의 전위범위에서 $0.25mA/cm^2$으로 15 cycle 동안 충 방전 실험한 결과 $900^{\circ}C$에서 합성된 스피넬 구조의 $LiMn_2O_4$는 82 mAh/g에서 50 mAh/g으로 용량 감소가 나타났으나 $850^{\circ}C$에서 합성한 $LiMn_2O_4$는 102~64 mAh/g을 유지했다.

• 한국세라믹학회지
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• 제37권6호
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• pp.552-558
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• 2000

LiMn2O4 thin fiolm cathodes for Li-ion secondary battery were fabricated by r.f. magnetron sputtering technique. As-deposited films were amorphous. A spinel structure could not be obtained LiMn2O4 films by in-situ thermal annealing. After post thermal annealing over $700^{\circ}C$ in oxygen atmosphere, LiMn2O4 films prepared above 100 W r.f. power could be crystallized into a spinel structure. The electrochemical property of the LiMn2O4 film cathodes was tested in a Li/1 M LiClO4 in PC/LiMn2O4 cell. From cyclic voltammetry at scan rate of 2mV/sec of 2.5~4.5V, LiMn2O4 electrode prepared by post annealing at 75$0^{\circ}C$ showed good initial capacity. LiMn2O4 electrode prepared by post annealing at 80$0^{\circ}C$ showed the best crycling performance.

• 공업화학
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• 제9권5호
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• pp.774-780
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• 1998

스피넬 구조인 $LiMn_2O_4$의 안정성을 향상시키기 위해서 망간과 비슷한 이온반경을 갖는 여러 가지 금속원소, Mg, Fe, V, W, Cr, Mo들을 일부 치환하였으며 ($LiM_xMn_{2-x}O_4(0.05{\leq}x{\leq}0.02)$), 이 결과 $LiM_xMn_{2-x}O_4$ 정극은 정극물질로 사용할 경우 $LiMn_2O_4$보다 낮은 용량감소를 나타냈다. 그리고 화학확산계수의 측정 결과 $LiMg_{0.05}Mn_{1.9}O_4$와 $LiCr_{0.1}Mn_{1.9}O_4$의 화학확산계수는 $LiMn_2O_4$보다 약 10배 이상 크게 나타났다. 이러한 결과를 볼 때 $LiMn_2O_4$에 여러 가지 금속원소를 치환시킴으로 구조적인 안정화로 인한 전기화학적 성능을 향상시킬 수 있었다.

• 한국전기전자재료학회논문지
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• 제14권4호
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• pp.316-322
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• 2001

Cathode materials $LiMn_{2-y}$$M_{y}$ $O_4$(M=Zn and Mg) were obtained by reacting the mixture of LiOH.$H_2O$, Mn $O_2$ and MgO ar ZnO at 80$0^{\circ}C$ for 36h in an air atmosphere. These materials showed an extended cycle life in lithium-anode cells working at room temperatue in a 3.0 to 4.3V potential window. Among these materials, LiM $n_{1.9}$M $g_{0.1}$ $O_4$ showed the best cycle performance in terms of the capacity and cycle life. The discharge capacities of the cathode for the Li/LiM $n_{1.9}$ $M_{0.1}$ $O_4$ cell at the 1st cycle and at the 70th cycle were about 120 and 105mAh/g, respectively. This cell capacity is retained by 88% after 70th cycle. In cyclic voltammetry measurement, all cells revealed tow oxidation peaks and reduction peaks. However, Li/$LiMn_{2-y}$$M_{y}$ $O_4$ cell substituted with Zn and Mg showed new reaction peak during reduction reaction.eaction.ion.ion.

• 한국전기전자재료학회논문지
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• 제14권4호
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• pp.309-315
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• 2001

Crystallized $LiMn_{2-y}Mg_{y}O_4$ powder was prepared by calcing the mixture of LiOH.$H_2O$, $MnO_2$ and MgO at $800^{\circ}C$ for 36h in an air atmosphere. The structure of $LiMn_{2-y}Mg_{y}O_4$ crystallites was analyzed from powder X-ray diffraction data as a cubic spinel, space group Fd3m. Though all cathode material showed spinel phase based on cubic phase in X-ray diffraction, other peaks gradually exhibited and became intense with increasing y value in $LiMn_{2-y}Mg_{y}O_4$. However, ununiform which calculated by (111) face and (222) face was constant in spite of the increase of y value, except pure $LiMn_2O_4$. AC impedance of Li/$LiMn_{2-y}Mg_{y}O_4$ cells revealed the similar resistance of about $70\Omega$ before cycling. In addition, The impedance of Li/$LiMn_{1.9}Mg_{0.1}O_4$ cell changed during charge and discharge or after cycling.

• 한국세라믹학회지
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• 제48권6호
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• pp.531-536
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• 2011

Al doped $LiMn_2O_4$ ($LiMn_2O_4:Al$) synthesized by several Al doping process and Solid State method. The Al contents in $Mn_{1-x}Al_xO_2$ for $LiMn_2O_4:Al$ were analyzed 1.7 wt% by EDS. The $LiMn_2O_4:Al$ confirmed cubic spinel structure and approximately 5 ${\mu}m$ particles regardless of three kinds of doping process by solid state method. In the result of electrochemical performances, initial discharge capacity had 115 mAh/g in case of $LiMn_2O_4$ and 111 mAh/g of $LiMn_2O_4:Al$ after 100th cycle at room temperature. But the capacity retention results showed that $LiMn_2O_4$ and $LiMn_2O_4:Al$ were 44% and 69% respectively in the 100th cycle at 60$^{\circ}C$. Therefore we are confirmed that $LiMn_2O_4:Al$ increased the capacity retention about 25% than $LiMn_2O_4$, thus the effect of Al dopping on $LiMn_2O_4$ capacity retention.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2001년도 하계학술대회 논문집
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• pp.455-458
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• 2001

Spinel $LiMn_{2-y}$$M_{y}$ $O_4$powder was prepared solid-state method by calcining the mixture of LiOH - $H_2O$, Mn $O_2$, ZnO and MgO at 80$0^{\circ}C$ for 36h. To investigate the effect of substitution with Mg, Zn cation, charge-discharge experiments and initial impedance spectroscopy performed. The structure of $LiMn_{2-y}$$M_{y}$ $O_4$crystallites was analyzed from powder X-ray diffraction data as a cubic spinel, space group Fd3m. all cathode material showed spinel phase based on cubic phase in X-ray diffraction. Ununiform which calculated by (111) face and (222) face was constant in spite of the change of y value, except PUf\ulcorner LiM $n_2$ $O_4$. The discharge capacities of the cathode for the cation subbstitUtes $LiMn_{2-y}$$M_{y}$ $O_4$/Li cell at the 1st cycle and at the 40th cycle were about 120~124 and 108~112mAh/g except LiM $n_{1.9}$Z $n_{0.1}$ $O_4$/Li cell, respectively. This cell capacity is retained by 93% after 40th cycle. AC impedance of $LiMn_{2-y}$$M_{y}$ $O_4$/Li cells revealed the similar resistance of about 65~110$\Omega$ before cycling. before cycling.g.g.