• Applied Chemistry for Engineering
• /
• v.10 no.1
• /
• pp.80-84
• /
• 1999

$Li_{4/3}Mn_{5/3}O_4$ having a defect structure was prepared by sol-gel process using lithium acetate and manganese acetate as starting materials, and their electrode characteristics in the lithium secondary battery was investigated. The reaction mole ratio was determined as $AA/Mn(OAc)_2$ of 0.2 and $NH_4OH/Mn(OAc)_2$ to $H_2O/Mn(OAc)_2$ of 0.4. The product was obtained through heat treatment at $350^{\circ}C$ for 12hrs after 1'st heat treatment at $150^{\circ}C$ of xerogel under oxygen atmosphere. When the charge and discharge cycles were performed between 2.0 V and 3.2 V, $Li/Li_{4/3}Mn_{5/3}O_4$ cell showed the dicharge capacity of 84.23 mAh/g and the good cycleability was obtained in the plateau region.

• Journal of the Korean Electrochemical Society
• /
• v.13 no.2
• /
• pp.103-109
• /
• 2010

$Li_4Mn_5O_{12}$ was synthesized by combustion method using $LiNO_3$, $Li(CH_3COO){\cdot}2H_2O$ and $Mn(CH_3COO)_2{\cdot}4H_2O$. $Li_4Mn_5O_{12}$ was obtained over $400^{\circ}C$, however, the sample calcined at $400^{\circ}C$ for any time was mixed phases of $Li_4Mn_5O_{12}$ and $Mn_2O_3$. $Li_4Mn_5O_{12}$ calcined at $400^{\circ}C$ for 5 h had larger first discharge capacity (41.5mAh/g) at 1C-rate for 3.7~4.4V than other calcined samples. Moreover, applying to hybrid capacitor, it had good discharge capacity (24.74 mAh/g or 10.46 mAh/cc) at 100 mA/g for 1~2.5 V and higher energy density (39Wh/kg or 16.49Wh/cc) at same condition.

• Journal of Electrochemical Science and Technology
• /
• v.4 no.1
• /
• pp.34-40
• /
• 2013

The structural and electrochemical properties of $Li_{0.99}Ni_{0.46}Mn_{1.56}O_4$ ($Fd{\bar{3}}m$, disordered spinel) cathode material were studied and compared with stoichiometric $LiNi_{0.5}Mn_{1.5}O_4$ ($P4_332$, ordered spinel). First cycle discharge capacity of $Li_{0.99}Ni_{0.46}Mn_{1.56}O_4$ was similar to that of $LiNi_{0.5}Mn_{1.5}O_4$ at C/3 and 1C rate, but cycling performance of $Li_{0.99}Ni_{0.46}Mn_{1.56}O_4$ was better than that of $LiNi_{0.5}Mn_{1.5}O_4$ especially at high rate of 1C. This can be explained by performing synchrotron based in-situ XRD and results of GITT measurements. It is considered that faster lithium ion diffusion in the $Li_{0.99}Ni_{0.46}Mn_{1.56}O_4$ cathode results in the improvement of the rate capability. To study structural changes during cycling, synchrotron in-situ XRD patterns of both the samples were recorded at C/3 and 1C rate. Compared to stoichiometric $LiNi_{0.5}Mn_{1.5}O_4$, disordered $Li_{0.99}Ni_{0.46}Mn_{1.56}O_4$ spinel sample has pseudo one phase behavior and one step phase transition between two cubic phases. So, $LiNi_{0.5}Mn_{1.5}O_4$ would experience a much greater strain and stress, originating from the two phase transitions between three cubic phases and suffer from capacity loss during cycling especially at high rate.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
• /
• v.29 no.5
• /
• pp.298-302
• /
• 2016

In this work, $LiMn_2O_4$ and $LiNi_{1/3}Mn_{1/3}Co_{1/3}O_2$ cathode materials are mixed by some specific ratios to enhance the practical capacity, energy density and cycle performance of battery. At present, the most used cathode material in lithium ion batteries for EVs is spinel structure-type $LiMn_2O_4$. $LiMn_2O_4$ has advantages of high average voltage, excellent safety, environmental friendliness, and low cost. However, due to the low rechargeable capacity (120 mAh/g), it can not meet the requirement of high energy density for the EVs, resulting in limiting its development. The battery of $LiMn_2O_4-LiNi_{1/3}Mn_{1/3}Co_{1/3}O_2$ (50:50 wt%) mixed cathode delivers a energy density of 483.5 mWh/g at a current rate of 1.0 C. The accumulated capacity from $1^{st}$ to 150th cycles was 18.1 Ah/g when the battery is cycled at a current rate of 1.0 C in voltage range of 3.2~4.3 V.

• Journal of the Korean Electrochemical Society
• /
• v.8 no.4
• /
• pp.172-176
• /
• 2005

Recently, many researches on the high-voltage 5 V class cathode material have focused on $LiNi_{0.5}Mn_{1.5}O_4$, where $Mn^{3+}$ in the existing $LiMn_2O_4 (Li[Mn^{3+}][Mn^{4+}]O_4)$ is replaced by $Ni^{2+}(Li[Ni^{2+}]_{0.5}[Mn^{4+}]_{1.5}O_4)$ in order to utilize $Ni^{2+}/Ni^{4+}$ redox reaction in the 5V region. The partial substitution of Mn in $LiMn_2O_4$ for other transition metal element, $LiM_yMn_{1-y}O_4$(M=Cr, Al, Ni, Fe, Co, Cu, Ga etc) is known as a good solution to overcome the problems associated with $LiMn_2O_4$ like the gradual capacity fading. In this study, we synthesized $LiNi_{0.5}Mn_{1.5}O_4$ through a mechanochemical process and investigated its morphological, crystallographic and electrochemical characteristics. The results showed that 4 V peaks had been found in the cyclic volammograms of the synthesized powders due to the existence of $Mn^{3+}$ from the incomplete substitution of $Ni^{2+}$ for $Mn^{3+}$ implying that the mechanochemical activation alone was not good enough to synthesize an exact stoichiometric compound of $LiNi_{0.5}Mn_{1.5}O_4$. The synthetic condition of mechanochemical process, such as type of starting materials, ball-mill and calcination condition was optimized for the best electrochemical performance.

• Journal of the Korean Crystal Growth and Crystal Technology
• /
• v.11 no.4
• /
• pp.154-159
• /
• 2001

(Li,Al)$MnO_2(OH)_2$:Co compound was synthesized by hydrothermal method. $MnO_2$, LiOH.$H_2$O, $Co_3O_4$ and $Al(OH)_3$ were used as starting materials and the optimum conditions for synthesis of monolithic (Li,Al)$MnO_2(OH)_2$:Co compound were as follows : reaction temperature; $200^{\circ}C$, reaction time; 3 days, hydrothermal solvent; 3M-KOH solution, reaction apparatus; seesaw type, atomic ratio of Li:Al:Mn;Co = 1:2.1:2.5~2:0.5~1. Monolithic(Li,Al)$MnO_2(HO)_2$:Co compound synthesized in this work had a god crystallinity and excellent color forming effect as a blue pigment compatible with natural mineral. The particles of the synthesized (Li,Al)$MnO_2(OH)_2$:Co compound have hexagonal plate shape with the size of 0.5~1 $\mu\textrm{m}$.

• Applied Chemistry for Engineering
• /
• v.9 no.2
• /
• pp.220-225
• /
• 1998

The spinel structured $LiMn_2O_4$ was prepared from $Li_2CO_3$ and $MnO_2$ by calcination at various temperatures in the range of $750{\sim}900^{\circ}C$. It was found that the most suitable cubic structure of $LiMn_2O_4$ was obtained by heating at $850^{\circ}C$ for 12 hrs. However, in the calcination at $900^{\circ}C$, $Mn^{4+}$ of 0.06M was changed to $Mn^{+3}$ by the oxygen loss, so that it has been shown that the formula has changed to $LiMn_2O_{3.97}$. This phenomena were in agreement with the Jahn-Teller distortion by the increment of $Mn^{+3}$ ion on the octahedral sites of the spinel structured $LiMn_2O_4$. The results showed that after 15 charge/discharge cycles in the voltage range from 3.5V to 4.3V versus Li/$Li^+$ with a current density of $0.25mA/cm^2$, the spinel structured $LiMn_2O_4$ that was prepared at $900^{\circ}C$ showed a lower discharge capacity, 82~50 mAh/g, while the $LiMn_2O_4$, prepared at $850^{\circ}C$, showed the discharge capacity of 102~64 mAh/g.

• Journal of the Korean Ceramic Society
• /
• v.38 no.5
• /
• pp.424-430
• /
• 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.

• Korean Chemical Engineering Research
• /
• v.40 no.6
• /
• pp.752-756
• /
• 2002

Green-emitting $Zn_2SiO_4:Mn$ phosphors for PDP(Plasma Display Panel) application were synthesized by colloidal seed-assisted spray pyrolysis process. The codoping with $Gd^{3+}/Li^+$, which replaces $Si^{4+}$ site in the willemite structure, was performed to improve the luminous properties of the $Zn_2SiO_4:Mn$ phosphors. The particles prepared by spray pyrolysis process using fumed silica colloidal solution had a spherical shape, small particle size, narrow size distribution, and non-aggregation characteristics. The $Gd^{3+}/Li^+$ codoping amount affected the luminous characteristics of $Zn_2SiO_4:Mn$ phosphors. The codoping with proper amounts of $Gd^{3+}/Li^+$ improved both the photoluminescence efficiency and decay time of $Zn_2SiO_4:Mn$ phosphor particles. In spray pyrolysis, the post-treatment temperature is another factor controlling the luminous performance of $Zn_2SiO_4:Mn$ phosphors. The $Zn_{1.9}SiO_4:Mn_{0.1}$ phosphor particles containing 0.1 mol% $Gd^{3+}/Li^+$ co-dopant had a 5% higher PL intensity than the commercial product and 5.7 ms decay time after post-treatment at $1,145^{\circ}C$.

• Korean Journal of Metals and Materials
• /
• v.46 no.3
• /
• 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.