• Applied Chemistry for Engineering
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• v.9 no.5
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• pp.774-780
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• 1998

For the stabilization of the spinel structured $LiMn_2O_4$, a fraction of manganese was substituted with various metals such as Mg, Fe, V, W, Cr, Mo with Mn that had a similar ionic radii ($LiM_xMn_{2-x}O_4(0.05{\leq}x{\leq}0.02)$). The $LiM_xMn_{2-x}O_4$ showed a substantial improvement as lower capacity loss than that of the spinel structured $LiMn_2O_4$ when it was used as a cathode material. And with the partial substitution, the chemical diffusion coefficient for $LiMg_{0.05}Mn_{1.9}O_4$ and $LiCr_{0.1}Mn_{1.9}O_4$ was increased by and order of magnitude compared to that of the $LiMn_2O_4$ with spinel structure. The results showed that significant improvement can be made on the electrochemical characteristics as the structure of the $LiMn_2O_4$ electrode material was stabilized by the partial substitution.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 1999.05a
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• pp.133-136
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• 1999

We report on the electrochemical properly of LiZ $n_{x}$Mn $_{2-x}$ $O_4$ for different degrees of Zn substitution(x) Though all cathode material showed spinel phase based on cubic phase in X-ray diffraction, other peaks(M $n_2$ $O_3$ or M $n_3$ $O_4$) gradually exhibited and became intense with the increase of x vague in LiZ $n_{x}$Mn $_{2-x}$ $O_4$. In addtion, TG-DTA analysis exhibited that both LiM $n_2$ $O_4$ and LiZ $n_{0.1}$ M $n_{1.9}$ $O_4$ occurred the weight loss(TG) and the endothermic and exothermic reaction(DTA) until 80$0^{\circ}C$ When x=0.1 in LiZ $n_{x}$Mn $_{2-x}$ $O_4$ cathode materials showed the charge and discharge capacity of about 100mAh/g at first cycle and about 70mAh/g after tooth cycle.cle.e.cle.e.e.e.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 1999.11a
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• pp.387-390
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• 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.

• Applied Chemistry for Engineering
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• v.10 no.6
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• pp.832-837
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• 1999

Stability of a cathode material was determined by Tafel plot in 1 M LiOH solution. The stabilized $LiM_xMn_{2-x}O_4$ (x=0.05~0.1) electrode resulted in overpotential of 0.13~0.15 mV at 100 mA. This overpotential was 0.05 mV lower than that of the spinel structured $LiMn_2O_4$ electrode. Conductivity test at various potentials showed that the conductivity of $LiM_xMn_{2-x}O_4$ was higher than that of the spinel structured $LiMn_2O_4$ and the bulk resistance of $LiM_xMn_{2-x}O_4$ due to the dissolution of $Mn^{2+}$ was lowered.

• Journal of the Korean Electrochemical Society
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• v.11 no.3
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• pp.197-210
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• 2008

The cathode materials for lithium ion battery have been developed in accordance with the battery performance. $LiCoO_2$ initially adapted at lithium ion battery is going to be useful even at the charging voltage of 4.3 V by surface treatment or doping which drastically improved the performance of $LiCoO_2$. On the other hand, the complicate and multiple functions of recent electronic equipments required higher operational voltage and higher capacity than ever, which is going to be driving force for developing new cathode materials. Some of them are $LiNi_{1-x}{M_xO_2}$, $Li[Ni_{x}Mn_{y}Co_{z}]O_{2}$, $Li[{Ni}_{1/2}{Mn}_{1/2}]O_{2}$. Other new type of cathode materials having high safety is also developed to apply for HEV (hybrid electrical vehicle) and power tool applications. ${LiMn}_{2}{O}_{4}$ and $LiFePO_4$ are famous for highly stable material, which are expected to give contribution to make safer battery. In near future, the various materials having both capacity and safety will be developed by new technology, such as solid solution composite.

• Journal of the Korean Electrochemical Society
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• v.7 no.1
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• pp.1-8
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• 2004

This paper deals with the recent development of high-voltage cathode materials of mono- and di- metal ions substituted spinel $LiMn_2O_4$ for lithium batteries. $LiCu_xMn_{2-x}O_4(0{\leq}x{\leq}0.5)$ shows reversible intercalation/deintercalation in two potential regions, $3.9\~43\;and\;4.8-5.0V$ and stable electrochemical cycling behavior but with low capacity. $LiNi_{0.5}Mn_{1.5}O_4$ obtained by a sol-gel process delivers a capacity of 127mAh $g^{-1}$ on the first cycle and sustains a value of 124 mAh $g^{-1}$ even after the 60th cycle. The $Li_xCr_yMn_{2-y}O_4(0{\leq}x{\leq}0.5)$ solid-solutions exhibit enhanced specific capacity, larger average voltage, and improved cycling behaviors for low Cr content. $LiCr_yMn_{2-y}O_4$ presents a reversible Li deintercalation process at 4.9V, whose capacity is proportional to the Cr content in the range of $0.25{\leq}x{\leq}0.5$ and delivers higher capacities. $LiM_yCr_{0.5-y}Mn_{1.5}O_4(M=Fe\;or\;Al)$ shows that the capacity retention is lowered compared with lithium manganate. The cumulative capacities obtainable with Al-substitutted materials are less than those with Fe-substituted materials. $LiCr_xNi_{0.5-x}Mn_{1.5}O_4(x=0.1)$ delivers a high initial capacity of 1$152mAh\;g^{-1}$ with excellent cycleability.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2001.07a
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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.

• Journal of the Korean Electrochemical Society
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• v.10 no.4
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• pp.239-244
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• 2007

In order to investigate the effect of fluorine ion in the $Li_{1-x}FeO_2Li_xMnO_2$ (Mn/(Mn + Fe) = 0.8) cathode material, it was synthesized $Li_{1-x}FeO_{2-y}F_y-Li_xMnO_2$ (Mn/(Mn + Fe) = 0.8, $0.05{\le}y{\le}0.15$) cathode materials at $350^{\circ}C$ for 10hrs using solid-state method. $Li_{1-x}FeO_{2-y}F_y-Li_xMnO_2$ (Mn/(Mn + Fe) = 0.8, $0.0{\le}y{\le}0.1$ was composed many large needle-like particles of about $1-1.5\;{\mu}m$ and small particles of about 50-100 nm, which were distributed among the larger particles. However, $Li_{1-x}FeO_{1.85}F_{0.15}-Li_xMnO_2$ material showed slightly different particle morphology. The particles of $Li_{1-x}FeO_{1.85}F_{0.15}-Li_xMnO_2$ were suddenly increased and started to be a spherical type of particle shape. $Li/Li_{1-x}FeO_{1.9}F_{0.1}-Li_xMnO_2$ cell showed a high initial discharge capacity of 163 mAh/g and a high cycle retention rate of 95% after 50 cycles. The initial discharge capacity of $Li/Li_{1-x}FeO_{2-y}F_y-Li_xMnO_2$ ($0.05{\le}y{\le}0.15$) cells increased according to the increase of F content. However, the cycleability of this cell was very rapidly decreased when the substituted fluorine content is over 0.1. We suggested that too large amount of F ion fail to substitute into the $Li_{1-x}FeO_2-Li_xMnO_2$ structure, which resulted in the severe decline of battery performance.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.14 no.5
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• pp.383-390
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• 2001

We have investigated the L $i_{1+x}$M $n_2$ $O_4$system as a cathode material for lithium rechargeable batteries. To improve the cycle performance of spinel LiM $n_2$ $O_4$ as the cathode of 4V class lithium secondary batteries, spinel phase L $i_{1+x}$M $n_2$ $O_4$(x=0, 0.025, 0.05, 0.075) was prepared at 75$0^{\circ}C$ for 48h. The preparation of L $i_{1+x}$M $n_2$ $O_4$ from L $i_2$ $O_3$ and Mn $O_2$ under air is studied. The compounds were synthesized by using solid-state reaction. Structural refinements were carried out with a Rietveld-refinement program. Electrochemical properties were examined using the Li/L $i_{1+x}$M $n_2$ $O_4$ cells. The capacity of L $i_{1+x}$M $n_2$ $O_4$ decreases with increases lithium content, while the cycle life improves. The initial discharge capacity are 118mAh/g and 116mAh/g for LiM $n_2$ $O_4$ decreases with increases lithium content, while the cycle life improves. The initial discharge capacity are 118mAh/g and 116mAh/g for LiM $n_2$ $O_4$ and L $i_{1.025}$M $n_2$ $O_4$, respectively.pectively.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.14 no.4
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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.