• 한국전기전자재료학회:학술대회논문집
• /
• 한국전기전자재료학회 1999년도 추계학술대회 논문집
• /
• pp.387-390
• /
• 1999

To improve the cycle performance LiM $n_2$ $O_4$as the cathode of 4V class lithium secondary batteries, the cathode properties of the cubic spinel phases LiM $g_{x}$ /M $n_{2-x}$/ $O_4$ synthesized at 80$0^{\circ}C$ were examined. All cathode material showed spinel phase based on cubic phase in X-ray diffraction however. other peaks gradually exhibited and became intense with the increase of x value in LiM $g_{x}$ /M $n_{2-x}$/ $O_4$. The cycle performance of the LiM $g_{x}$ /M $n_{2-x}$/ $O_4$was improved by the substitution of $Mg^{2+}$ for M $n^{3+}$ in the octahedral sites. Specially LiM $g_{0.1}$/M $n_{1.9}$ / $O_4$cathode materials showed the charge and discharge capacity of about 130~125mAh/g at first cycle and about 105mAh/g after 50th cycle. It is excellent than that of pure LiM $n_{2}$/ $O_4$ which 125mAh/g at first cycle 70mAh/g at 50th. In addition cathode material prepared at 80$0^{\circ}C$ for 24hr and 42hr in the charge and discharge capapcity as well as the cycle stability.ility.y.y.

• 대한금속재료학회지
• /
• 제46권3호
• /
• pp.174-181
• /
• 2008

The stability of the cathode materials for Li secondary battery is an important factor for its cyclability. The present paper focuses on the structural stability of $LiNi_{0.5}Mn_{1.5}O_4$ during lithiation/delithiation of Li ions and compared to that of $LiMn_{2}O_4$. $LiMn_{2}O_4$ and $LiNi_{0.5}Mn_{1.5}O_4$ powders are synthesized using a solgel method and their structural and electrochemical properties are investigated by XRD, SEM, and charge-discharge tests. $Li_xMn_2O_4$ and $Li_xNi_{0.5}Mn_{1.5}O_4$(x = 0.9,0.5,0.1) specimens are obtained after charge/discharge tests by controlling the cut-off voltage for XRD and TEM investigation. The charge-discharge tests shows that initial capacity of $LiNi_{0.5}Mn_{1.5}O_4$ is 125 mAh/g and that of LiMn2O4 is around 100 mAh/g. The capacity of $LiNi_{0.5}Mn_{1.5}O_4$ is maintained 95% of its initial capacity whereas the capacity of $LiMn_{2}O_4$ is maintained 65% of its initial capacity.

• 한국재료학회지
• /
• 제12권4호
• /
• pp.274-278
• /
• 2002

Discrete-variational(DV)-$X{\alpha}$ method was applied to investigate the electronic structures of spinel- type manganese oxide which is well known to the high performance adsorbent or cathode material for lithium ion. The results of DOS(density of states) and Mulliken population analysis showed that Li was nearly fully ionized and interactions between Mn and O were strong covalent bond. The effective charge of Li and Mn was +0.77 and +1.44 respectively and the overlap population between Mn and O was 0.252 in $LiMn_2O_4$. These results from DV-X$\alpha$ method were well coincided with the experimental result by XPS analysis and supported the feasibility of theoretical interpretation for the $LiMn_2O_4$ compound.

• 전기화학회지
• /
• 제8권2호
• /
• pp.82-87
• /
• 2005

고전압 용 양극산화물 $LiNi_{0.5}Mn_{1.5}O_4$는 고온에서 합성 시, 입자 내에 산소결함에 의한 불순물상을 만들게 된다. 불순물상은 불완전한 스피넬 구조를 형성하며 리튬이온의 삽입$\cdot$탈리를 방해하여 전극의 성능을 감소시킨다. 본 연구에서는 고온 열처리 시 생성되는 이러한 불순물상의 거동을 파악하기 위해 크롬을 치환한 $LiNi_{0.5-x}Mn_{1.5}Cr_xO_4(0{\leq}x{\leq}0.05)$를 졸$\cdot$겔법을 이용하여 합성하여 고온 열분석을 실시하였다. 열분석 결과 크롬이 치환되지 않은 양극활물질은 산소결함에 의한 $2\%$의 무게 감소를 보였으나, 크롬이 치환된 경우 무게 감소분이 줄어들어 불순물 생성이 억제됨을 알 수 있었다. XRD 분석에서도 크롬이 치환된 경우 불순물 상이 억제됨을 나타내었으며 불순물상의 감소로 인해 크롬을 첨가한 양극활물질 $LiNi_{0.5-x}Mn_{1.5}Cr_xO_4$를 사용한 경우 충·방전 실험 시 가역 용량과 싸이클 안정성이 향상됨을 볼 수 있었다.

• 한국전기전자재료학회논문지
• /
• 제15권4호
• /
• pp.361-366
• /
• 2002

Spinel $LiMn_{2-y}M_yO_4$ and $LiMn_{2-y}M_yO_4$ (M=Mg, Zn) powders were synthesized by solid-state method at $800^{\circ}C$ for 37h. Crystal structure and electrochemical properties were analyzed by X-ray diffraction, charge-discharge test, cyclic voltammetry and ac impedance to $LiMn_{2-y}M_yO_4$. All cathode material showed spinel structure in X-ray diffraction. Ununiform distortion which calculated by (111) face and (222) face was almost constant in spite of the change of the kind and the substituting ratio of the metal cation in $LiMn_{2-y}M_yO_4$ (M=Mg, Zn). $LiMn_{1.9}Mg_{0.05}Zn_{0.05}O_4/Li$ cell substituted $Mg^{+2}$ and $Zn^{+2}$ showed excellent discharge capacities than other cells, which it presented about 120mAh/g at the 1st cycle and about 73mAh/g at the 250th cycle, respectively. AC impedance of $LiMn_{2-y}M_yO_4/Li$ cells showed the similar resistance of about 65~110$\Omega$ before cycling.

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

• Bulletin of the Korean Chemical Society
• /
• 제18권11호
• /
• pp.1153-1158
• /
• 1997

The powder characteristics of LiMn2O4 prepared by the citrate sol-gel method have been investigated. The optimum pH for the preparation of homogeneous citrate gel was calculated by the theoretical consideration of thermodynamic equilibrium constants for metal-citrate complexes and metal salts. The obtained citrate gel was prefired at 300 ℃ and calcined at 300-700 ℃ for 1 h. The obtained powders were characterized by TG/DSC, FT-IR spectrometer, X-ray diffractometer, SQUID magnetometer, SEM, and particle size analyzer. It was observed that the mixed phases of spinel LiMn2O4 and Mn3O4 were transformed into spinel LiMn2O4 phase and the vibrational bands due to the carbonate and nitrate were also disappeared over 400 ℃. At temperatures below 150 K, inverse molar susceptibilities of every sample began to show an antiferromagnetic ordering of Mn magnetic moments.

• 전기화학회지
• /
• 제10권1호
• /
• pp.48-51
• /
• 2007

리튬이온전지의 스피넬형 양극활물질 $LiMn_2O_4$의 입자 크기 및 비표면적의 전기화학 특성상의 영향을 고찰하기 위하여 스피넬 물질을 공침법과 고상법에 의해 합성되었다. X-선 회절분석을 통하여 합성된 두 물질 모두 Fd3m space group을 갖는 스피넬 구조가 형성된 것을 확인하였다. 공침법을 사용하여 얻은 물질은 상대적으로 높은 충진 밀도와 균일한 입도 분포를 갖는 구형의 분말이었다. 그러나 고상법을 사용하여 얻은 활물질은 비교적 입자 크기가 작고 넓은 입도분포를 나타내었다. 측정된 두 물질의 비표면적(BET)은 각각 $0.8m^2g^{-1}$(공침법)과 $3.6m^2g^{-1}$(고상법)로 큰 차이를 보였다. 두 물질의 전기화학적 특성을 평가하기 위하여 코인타입(CR2032)전지를 제작하여 고온($55^{\circ}C$)에서 충 방전테스트를 하였다. 공침법으로 합성된 물질의 고온에서 방전용량 유지율은 50사이클 이후 고상법으로 합성된 물질의 68.3% 보다 14% 향상된 82.3%로 향상된 방전용량 유지율을 보였다.

• Journal of Magnetics
• /
• 제19권3호
• /
• pp.210-214
• /
• 2014

The effects of manganese substitution on the crystallographic and magnetic properties of Li-Zn-Cu ferrite, $Li_{0.5}Zn_{0.2}Cu_{0.4}Mn_xFe_{2.1-x}O_4$ ($0.0{\leq}x{\leq}0.8$), were investigated. Ferrites were synthesized via a conventional ceramic method. We confirmed the formation of crystallized particles using X-ray diffraction, field emission scanning electron microscopy and $M{\ddot{o}}ssbauer$ spectroscopy. All of the samples showed a single phase with a spinel structure, and the lattice constants linearly decreased as the substituted manganese content increased, and the particle size of the samples also somewhat decreased as the doped manganese content increased. All the $M{\ddot{o}}ssbauer$ spectra can be fitted with two Zeeman sextets, which are the typical spinel ferrite spectra of $Fe^{3+}$ with A- and B-sites, and one doublet. The cation distribution was determined from the variation of the $M{\ddot{o}}ssbauer$ parameters and of the absorption area ratio. The magnetic behavior of the samples showed that an increase in manganese content led to a decrease in the saturation magnetization, whereas the coercivity was nearly constant throughout. The maximum saturation magnetization was 73.35 emu/g at x = 0.0 in $Li_{0.5}Zn_{0.2}Cu_{0.4}Mn_xFe_{2.1-x}O_4$.

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