• Proceedings of the Korean Vacuum Society Conference
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• 2011.02a
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• pp.409-409
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• 2011

All solid-state thin film lithium batteries have many applications in miniaturized devices because of lightweight, long-life, low self-discharge and high energy density. The research of cathode materials for thin film lithium batteries that provide high energy density at fast discharge rates is important to meet the demands for high-power applications. Among cathode materials, lithium manganese oxide materials as spinel-based compounds have been reported to possess specific advantages of high electrochemical potential, high abundant, low cost, and low toxicity. However, the lithium manganese oxide has problem of capacity fade which caused by dissolution of Mn ions during intercalation reaction and phase instability. For this problem, many studies on effect of various transition metals have been reported. In the preliminary study, the Sn-substituted LiMn2O4 thin films prepared by pulsed laser deposition have shown the improvement in discharge capacity and cycleability. In this study, the thin films of LiMn2O4 and LiSn0.0125Mn1.975O4 prepared by RF magnetron sputtering were studied with effect of deposition parameters on the phase, surface morphology and electrochemical property. And, all solid-state thin film batteries comprised of a lithium anode, lithium phosphorus oxy-nitride (LiPON) solid electrolyte and LiMn2O4-based cathode were fabricated, and the electrochemical property was investigated.

• Journal of Electrochemical Science and Technology
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• v.13 no.2
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• pp.177-185
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• 2022

Electrochemical properties of LiMn₂O₄ cathode were investigated in three types of Zn-containing electrolytes: lithium-zinc sulfate electrolyte (1M ZnSO₄ / 2M Li₂SO₄), zinc sulfate electrolyte (2MZnSO₄) and lithium-zinc-manganese sulfate electrolyte (1MZnSO₄ / 2MLi₂SO₄ / 0.1MMnSO₄). Cyclic voltammetry measurements demonstrated that LiMn₂O₄ is electrochemically inactive in pure ZnSO₄ electrolyte after initial oxidation. The effect of manganese (II) additive in the zinc-manganese sulfate electrolyte on the electrochemical performance was analyzed. The initial capacity of LiMn₂O₄ is higher in presence of MnSO₄ (140 mAh g^-1 in 1 M ZnSO₄ / 2 M Li₂SO₄ / 0.1 M MnSO₄ and 120 mAh g^-1 in 1 M ZnSO₄ / 2MLi₂SO₄). The capacity increase can be explained by the electrodeposition of MnO_x layer on the electrode surface. Structural characterization of postmortem electrodes with use of XRD and EDX analysis confirmed that partially formed in pure ZnSO₄ electrolyte Zn-containing phase leads to fast capacity fading which is probably related to blocked electroactive sites.

• 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.

• Proceedings of the Korean Ceranic Society Conference
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• 2000.04a
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• pp.68.2-68.2
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• 2000

• Journal of Magnetics
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• v.19 no.3
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• pp.210-214
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• 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 $Li_{0.5}Zn_{0.2}Cu_{0.4}Mn_xFe_{2.1-x}O_4$.

• 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 Materials Research Society of Korea Conference
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• 2003.03a
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• pp.216-216
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• 2003

현재 상용화되어 있는 리튬 이차전지용 양극재료로는 비교적 작동전압이 높은 층상 암염구조(LiCoO$_2$, LiNiO$_2$) 및 Spinet계(LiMn$_2$O$_4$) 전이금속 산화물이 대부분 이용되고 있다 하지만 LiCoO$_2$나 LiNiO$_2$ 같은 상용화 물질은 비교적 높은 비용과, 강한 독성 때문에 많은 문제점을 가지고 있다. 또 Spinel(LiMn$_2$O$_4$)는 낮은 비용과 환경친화적인 장점에도 불구하고 Jahn-Teller 변형과 관련된 구조적 변형이 심각하기 때문에 사이클시 비가역적인 용량의 감소가 심각하다. 이러한 관점에서 전이금속보다 그 양이 풍부하고 저렴할 뿐만 아니라 독성이 없는 Olivine 구조 (LiFePO$_4$)를 갖는 phosphate계 화합물에 관심을 가지게 되었다. LiFePO$_4$는 리튬 음극과 3.4V의 방전전압을 나타내며, 170mAh/g의 이론용량을 가지고 있어, Fe-base의 장점은 물론 안정적인 결정구조 및 현재 상용화된 재료들과 비슷한 에너지 밀도를 가진다. 따라서 본 연구에서는 양극물질의 기존 두 제조법인 고상반응법과 sol-gel법으로 대표되는 제조법의 단점을 상호 보완될 수 있다고 판단되는 기계적 합금화법(Mechanical Alloying, MA)공정을 도입하여 초미세립 분말 제조에 초점을 맞추어 Olivine phosphate계 양극물질의 제조 및 전기화학적 특성을 연구하였다.

• Proceedings of the Korean Institute of Surface Engineering Conference
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• 1998.05a
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• pp.11-12
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• 1998

• Journal of the Korean Electrochemical Society
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• v.15 no.3
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• pp.172-180
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• 2012

The $LiMn_2O_4$ cathodes for lithium ion battery were synthesized from various precursors of manganese oxides and manganese hydroxides. As the first step, nanosized precursors such as ${\alpha}-MnO_2$ (nano-sticks), ${\beta}-MnO_2$ (nano-rods), $Mn_3O_4$ (nano-octahedra), amorphous $MnO_2$(nano-spheres), and $Mn(OH)_2$ (nano-plates) were prepared by a hydrothermal or a precipitation method. Spinel $LiMn_2O_4$ with various sizes and shapes were finally synthesized by a solid-state reaction method from the manganese precursors and LiOH. Nano-sized (500 nm) octahedron $LiMn_2O_4$ showed high capacities of 107 mAh $g^{-1}$ and 99 mAh $g^{-1}$ at 1 C- and 50 C-rate, respectively. Three dimensional octahedral crystallites exhibit superior electrochemical characteristics to the other one-dimensional and two-dimensional shaped $LiMn_2O_4$ nanoparticles. After 500 consecutive charge discharge battery cycles at 10 C-rate with the nano-octahedron $LiMn_2O_4$ cathode, the capacity retention of 95% was observed, which is far better than any other morphologies studied in this work.

• Journal of the Korean Ceramic Society
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• v.39 no.6
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• pp.523-527
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• 2002

LiMn$_2$O$_4$ compounds were synthesized by calcining a mixture of LiOH and MnO$_2$(CMD) at 47$0^{\circ}C$ for 10 h and then calcining again at $650^{\circ}C$ to 90$0^{\circ}C$ fur 48 h in air with intermediate grinding. All the synthesized samples exhibited XRD patterns for the cubic spinel phase with a space group Fd3m. The lattice parameter increased gradually as the sintering temperature rose. The electrochemical cells were charged and discharged fur 20 cycles at a current density 300$\mu$A/$\textrm{cm}^2$ between 3.5 V and 4.3 V. The voltage vs. discharge capacity curves for all the samples showed two plateaus. The LiMn$_2$O$_4$ sample calcined at 90$0^{\circ}C$ had the largest first discharge capacity. This sample exhibited the best crystallinity, had relatively large lattice parameter and had relatively large particles with rectatively homogeneous size. All the samples showed good cycling performances. Among all the samples, the LiMn$_2$O$_4$ calcined at 85$0^{\circ}C$ had relatively large first discharge capacity and very good cycling performance. The addition of excess LiOH and the mixing in ethanol considered to help the formation of the more LiMn$_2$O$_4$ phase per unit weight sample and the more stable LiMn$_2$O$_4$phase. These led to the larger discharge capacities and the better cycling performances. The cyclic voltammograms fur the second cycle of the LiMn$_2$O$_4$ samples showed the oxidation and reduction peaks around 4.05 V and 4.18 V and around 4.08 V and 3.94 V, respectively. The larger first discharge capacity of the sample calcined at the higher temperature is related to the larger lattice parameter.