• 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.

• Ceramist
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• v.21 no.4
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• pp.388-405
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• 2018

In this paper, we review about current development of electrode materials for Li-ion batteries and catalysts for fuel cells. We scrutinized various electrode materials for cathode and anode in Li-ion batteries, which include the materials currently being used in the industry and candidates with high energy density. While layered, spinel, olivine, and rock-salt type inorganic electrode materials were introduced as the cathode materials, the Li metal, graphite, Li-alloying metal, and oxide compound have been discussed for the application to the anode materials. In the development of fuel cell catalysts, the catalyst structures classified according to the catalyst composition and surface structure, such as Pt-based metal nanoparticles, non-Pt catalysts, and carbon-based materials, were discussed in detail. Moreover, various support materials used to maximize the active surface area of fuel cell catalysts were explained. New electrode materials and catalysts with both high electrochemical performance and stability can be developed based on the thorough understanding of earlier studied electrode materials and catalysts.

• Journal of the Korean Ceramic Society
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• v.42 no.4
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• pp.292-297
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• 2005

$LiMO_{2}(M=Co,Ni)$ samples were synthesized with $Li_{2}CO_{3},\;Co_{3}O_{4}$, and NiO by the solid-state reaction method. In the case of $LiCoO_{2}$, at low temperature$(T=400^{\circ}C)$ spinel structure was synthesized and the obtained spinel phase was transformed to layered phase at high temperature$(T\ge600^{\circ}C)$. The phase transition behaviors of $LiCoO_{2}$ were investigated with various heating temperature and time. The rate of transition was directly proportional to the concentrations of reactant, and activation energy of reaction was around 6.76 kcal/mol. When CoO(rock salt structure) was used as a starting material instead of $Co_{3}O_{4}$(spinel structure), layered structure of $LiCoO_{2}$ was obtained at low temperature. In the case of $LiNiO_{2}$ the transition from layered structure to rock salt structure occurred easily by disordering/ordering reaction, but did not occur in $LiCoO_{2}$. The difference in metal ion radii in $LiCoO_{2}$ and $LiNiO_{2}$ results in different behaviors of phase transitions.

• Journal of the Korean Electrochemical Society
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• v.10 no.1
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• pp.48-51
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• 2007

In order to investigate the effects of particle size and specific surface area(BET area) of spinel powder, $LiMn_2O_4$ were synthesized using metal oxide precursor by co-precipitation method(CoP) and solid state reaction (SSR) .X-ray diffraction(XRD) patterns revealed that the both prepared powder has a well developed spinel structure with Fd3m space group. The $LiMn_2O_4$ prepared by co-precipitation showed spherical morphology with narrow size distribution. However, the $LiMn_2O_4$ prepared by solid state reaction showed relatively smaller particles with irregular shape. The measured BET areas of the powers are $0.8m^2g^{-1}$ (CoP) and $3.6m^2g^{-1}$(SSR). The electrochemical performance of the Prepared $LiMn_2O_4$ powders was evaluated using coin type cells(CR2032) at elevated temperature ($55^{\circ}C$). The $LiMn_2O_4$ prepared by co-precipitation showed the better cycling performance(82.3%capacity retention at $50^{th}$ cycle) than that of the $LiMn_2O_4$(68.3%) prepared by solid state reaction at elevated temperature.

• Bulletin of the Korean Chemical Society
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• v.23 no.5
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• pp.679-682
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• 2002

Layered Na0.7[Ni0.05Mn0.95]O2 compounds have been synthesized by a sol-gel method, using glycolic acid as a chelating agent. Na0.7[Ni0.05Mn0.95]O2 precursors w ere used to prepare layered lithium manganese oxides by ion exchange for Na by Li, using LiBr in hexanol. Powder X-ray diffraction shows the layered Na0.7[Ni0.05Mn0.95]O2 has an O3 type structure, which exhibits a large reversible capacity of approximately 190 mA h g-1 in the 2.4-4.5 V range. Na0.7[Ni0.05Mn0.95]O2 powders undergo transformation to spinel during cycling.

• Journal of the Korean Electrochemical Society
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• v.12 no.1
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• pp.81-87
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• 2009

An indium-tin oxide (ITO) coated spinel manganese oxide (${LiMn_2}{O_4}$, LMO) is prepared and its high-temperature ($55^{\circ}C$) cycle performance and rate capability are examined. A severe electrolyte decomposition and film deposition is observed on the un-coated ${LiMn_2}{O_4}$ cathode, which leads to a significant electrode polarization and capacity fading. Such an electrode polarization is, however, greatly reduced for the ITO-coated (> 2 mol%) LMO cathode, which leads to an improved cycle performance. This can be rationalized by a suppression of electrolyte decomposition, which is in turn indebted to a decrease in the direct contact area between LMO and electrolyte. The suppression of film deposition on the ITO-coated LMO cathode is confirmed by infra-red spectroscopy. The rate capability is also improved by the surface coating, which may be resulted from a suppression of resistive film deposition and high electric conductivity of ITO itself.

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

• Applied Chemistry for Engineering
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• v.16 no.5
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• pp.689-692
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• 2005

In order to improve the electrochemical performances of Li-ion batteries when spinel $LiMn_2O_4$ is employed as a cathode active material, binary conductive agents were prepared using two different particle-sized carbons like Super P Black and $Vulcan^{(R)}$ XC-72R. The electrochemical performances of the $LiMn_2O_4$ cell system using binary conductive agents were evaluated in terms of specific charge and discharge capacities and cycle life. The cell with binary conductive agent in the 3:7 weight ratios of Super P Black and $Vulcan^{(R)}$ XC-72R showed better electrochemical performances due to the proper combination of ionic diffusion rate and electric contact.

• 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 Electrochemical Science and Technology
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• v.10 no.2
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• pp.223-230
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• 2019

A facile method for surface coating with $Li_2TiF_6$ which has a high lithium-ion conductivity, on $LiMn_2O_4$ spinel cathode material for high performance lithium ion batteries. The surface coating is performed by using a co-precipitation method with $Li_2CO_3$ powder and $H_2TiF_6$ solution under room temperature and atmospheric pressure without special equipment. Total coating amount of $Li_2TiF_6$ is carefully controlled from 0 to 10 wt.% based on the active material of $LiMn_2O_4$. They are evaluated by a systematic combination of analyses comprising with XRD, SEM, TEM and ICP. It is found that the surface modification of $Li_2TiF_6$ is very beneficial to high cycle life and excellent rate capability by reducing surface failure and supporting lithium ions transportation on the surface. The best coating condition is found to have a high cycle life of $103mAh\;g^{-1}$ at the 100th cycle and a rate capability of $102.9mAh\;g^{-1}$ under 20 C. The detail electrochemical behaviors are investigated by AC impedance and galvanostatic charge and discharge test.