• 한국전기화학회:학술대회논문집
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• 한국전기화학회 2002년도 전지기술심포지움
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• pp.57-65
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• 2002

The presence of tetragonal phase at the surface of $LiMn_2O_4$ pinicle due to a Jahn-Teller offset was previously reported to be one of the causes for capacity fading observed during cycling of $Li//Li_xMn_2O_4$ in 4V range. Further, it is reported that a Jahn-Teller effect in 4V range may be suppressed by substitution of Mn ions with Li ions or other transition metal ions. However, the direct evidence of the suppression of a Jahn-Teller effect in 4V range by substitution of Mn ions with other metal ions has not been reported. The dissolution and formation of surface film at the surface of $LiMn_2O_4$ electrodes also reportedly affect the capacity fading or rate capability. This study reports on the evidence of the onset and suppression of a Jahn-Teller effect in 4V range and the dissolution and formation of surface film at the surface of $LiMn_2O_4$ thin film electrodes using in situ bending beam method (BBM) in situ electrochemical quartz crystal microbalance (EQCM).

• Journal of Electrochemical Science and Technology
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• 제14권4호
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• pp.320-325
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• 2023

In Li-ion batteries, a thick electrode is advantageous for lowering the inactive current collector portion and obtaining a high energy density. One of the critical failure mechanisms of thick electrodes is inhomogeneous lithiation and delithiation owing to the axial location of the electrode. In this study, it was confirmed that the top layer of the composite electrode contributes more to the charging step owing to the high ionic transport from the electrolyte. A high-loading multilayered electrode containing LiFePO₄ (LFP) and LiNi_0.8Co_0.1Mn_0.1O₂ (NCM811) was developed to overcome the inhomogeneous electrochemical reactions in the electrode. The electrode laminated with LFP on the top and NCM811 on the bottom showed superior cyclability compared to the electrode having the reverse stacking order or thoroughly mixed. This improvement is attributed to the structural and interfacial stability of LFP on top of the thick electrode in an electrochemically harsh environment.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 1998년도 추계학술대회 논문집
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• pp.175-178
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• 1998

LiMn$_2$O$_4$-based spinels has been studied extensively as positive electrode materials for rechargeable lithium and lithium ion batteries. We describe here that LiMn$_2$O$_4$ cathode active materials is preparated by sol-gel process using water as solvent, which often yields inorganic oxides of excellent phase purity and well-controlled stoichiometry. Using this process, it has been possible to synthesize phase-pure crystalline spinel LiMn$_2$O$_4$ by calcining the appropriate precursors in air at 80$0^{\circ}C$ for several hours. The influence of different time have also been explored. LiMn$_2$O$_4$ preparated in the present study exhibit the single phase of cubic and active reaction at 400 ~ $600^{\circ}C$. Electrochemical studies show that the this method- synthesized materials appear to present reversible oxidation and reduction reactions at 3.0V ~ 4.5V and cycle stability during 50 cycle.

• 한국결정학회:학술대회논문집
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• 한국결정학회 2002년도 정기총회 및 추계학술연구발표회
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• pp.16-16
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• 2002

The presently commercialized lithium-ion batteries use layer structured LiCoO₂ cathodes. Because of the high cost and toxicity of cobalt, an intensive search for new cathode materials has been underway in recent years. Recently, a concept of a one-to-one solid state mixture of LiNO₂ and LiMnO₂, i.e., Li[Ni/sub 0.5/Mn/sub 0.5/]O₂, was adopted by Ohzuku and Makimura to overcome the disadvantage of LiNiO₂ and LiMnO₂. Li[Ni/sub 0.5/Mn/sub 0.5/]O₂ has the -NaFeO₂ structure, which is characteristic of the layered LiCoO₂ and LiNiO₂ structures and shows excellent cycleability with no indication of spinel formation during electrochemical cycling. Layered Li[Ni/sub x/Co/sub 1-2x/Mn/sub x/]O₂ (x = 0.5 and 0.475) materials with high homogeneity and crystallinity were synthesized using a mechanical alloying method. The Li[Ni/sub 0.475/Co/sub 0.05/Mn/sub 0.475/]O₂ electrode delivers a high discharge capacity of 187 mAh/g between 2.8 and 4.6 V at a high current density of 0.3 mA/㎠(30 mA/g) with excellent cycleability. The charge/discharge and differential capacity vs. voltage studies of the Li[Ni/sub x/Co/sub 1-2x/Mn/sub x/]O₂ (x = 0.5 and 0.475) materials showed only one redox peak up to 50 cycles, which indicates that structural phase transitions are not occurred during electrochemical cycling. The magnitude of the diffusion coefficients of lithium ions for Li[Ni/sub x/Co/sub 1-2x/Mn/sub x/]O₂(x = 0.5 and 0.475) are around 10/sup -9/ ㎠/s measured by the galvanostatic intermittent titration technique (GITT).

• Bulletin of the Korean Chemical Society
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• 제34권9호
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• pp.2573-2576
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• 2013

Rate capability and cyclability of $LiMn_2O_4$ should be improved in order to use it as a cathode material of lithium-ion batteries for hybrid-electric-vehicles (HEV). To enhance the rate capability and cyclability of $LiMn_2O_4$, it was coated with $MnV_2O_6$ by a sol-gel method. A $V_2O_5$ sol was prepared by a melt-quenching method and the $LiMn_2O_4$ coated with the sol was heat-treated to obtain the $MnV_2O_6$ coating layer. Crystal structure and morphology of the samples were examined by X-ray diffraction, SEM and TEM. The electrochemical performances, including cyclability at $60^{\circ}C$, and rate capability of the bare and the coated $LiMn_2O_4$ were measured and compared. Overall, $MnV_2O_6$ coating on $LiMn_2O_4$ improves the cyclability at high temperature and rate capability at room temperature at the cost of discharge capacity. The improvement in cyclability at high temperature and the enhanced rate capability is believed to come from the reduced contact between the electrode, and electrolyte and higher electric conductivity of the coating layer. However, a dramatic decrease in discharge capacity would make it impractical to increase the coating amount above 3 wt %.

• 한국결정성장학회지
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• 제10권3호
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• pp.219-225
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• 2000

스피넬형의 $LiMn_2$O$_4$는 출발물질로 LiOH와 Mn($CH_3$COO)$_2$.$4H_2$O를 사용하여 졸-겔법으로 합성한 xerogel을 $150^{\circ}C$로 1차 열처리한 후 $350^{\circ}C$로 2차 열처리하여 합성하였다. 그러나 $350^{\circ}C$ 이상으로 열처리할 경우 $Mn_2O_3$가 생겼으며, 이로 인해서 Li/lM $LiClO_4$(in PC)$LiMn_2O_4$cell을 구성하여 0.25 mA/$\textrm{cm}^2$의 전류밀도로 충.방전 실험을 한 결과 $350^{\circ}C$에서 열처리한 것은 15 cycle후에 88 mAh/g에서 56 mAh/g으로 35.7%의 용량감소가 나타났으나 $500^{\circ}C$에서 열처리한 것은 89 mAh/g에 51 mAh/g으로 42.5%의 용량감소가 나타났으며 이는 $Mn^{3+}$ 의 증가로 인한 Jahn-Teller distortion의 결과로 볼 수 있다.

• 한국세라믹학회지
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• 제41권10호
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• pp.735-741
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• 2004

단순화한 연소법에 의해 합성한 $LiMn_{1.92}Co_{0.08}O_4$와 $LiNi_{0.7}Co_{0.3}O_2$의 혼합물의 전기화학적 성질을 알아보기 위하여, 30분 동안 milling하여 $LiMn_{1.92}Co_{0.08}O_4$-x wt$\%$ $LiNi_{0.7}Co_{0.3}O_2$ (x=9, 23, 33, 41, and 47) 조성의 혼합물을 제조하였다. x=9 조성의 전극이 비교적 큰 초기방전용량(109.9mAh/g at 0.1C)과 좋은 싸이클 성능을 가지고 있었다. 싸이클링에 따른 혼합물 전극의 방전용량 감소는 주로 $LiNi_{0.7}Co_{0.3}O_2$의 퇴화에 기인한다고 생각된다. $LiNi_{0.7}Co_{0.3}O_2$의 퇴화는 $LiMn_{1.92}Co_{0.08}O_4$로부터 용해된 Mn이 $LiNi_{0.7}Co_{0.3}O_2$ 입자를 둘러싸서(coating) 일어나는 것으로 판단된다.

• Journal of Electrochemical Science and Technology
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• 제4권3호
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• pp.102-107
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• 2013

The electrochemical properties of Mg-doped $LiFe_{0.48}Mn_{0.48}Mg_{0.04}PO_4$ and pure $LiFe_{0.5}Mn_{0.5}PO_4$ olivine cathodes are examined and the lattice parameters are refined by Rietveld analysis. The calculated atomic parameters from the refinement show that $Mg^{2+}$ doping has a significant effect in the olivine $LiFeMnPO_4$ structure. The unit cell volume is 297.053(2) ${\AA}^3$ for pure $LiFe_{0.5}Mn_{0.5}PO_4$ and is decreased to 296.177(1) ${\AA}^3$ for Mg-doped $LiFe_{0.48}Mn_{0.48}Mg_{0.04}PO_4$ sample. The doping of $Mg^{2+}$ cation with atomic radius smaller than $Mn^{2+}$ and $Fe^{2+}$ ion induces longer Li-O bond length in $LiO_6$ octahedra of the olivine structure. The larger interstitial sites in $LiO_6$ octahedra facilitate the lithium ion migration and also enhance the diffusion kinetics of olivine cathode material. The $LiFe_{0.48}Mn_{0.48}Mg_{0.04}PO_4$ sample with larger Li-O bond length delivers higher discharge capacities and also notably increases the rate capability of the electrode.

• Journal of Electrochemical Science and Technology
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• 제9권2호
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• pp.93-98
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• 2018

$MnO_2$, a metal oxide used as an electrode material in electrochemical capacitors (EDLCs), has been applied in binary oxide and conducting polymer hybrid electrodes to increase their stability and capacitance. We developed a method for electrodepositing Mn-Ni oxide/PANI, Mn-Ni oxide/PEDOT, and Mn-Ni-Ru oxide/PEDOT films on carbon paper in a single step using a mixed bath. Mn-Ni oxide/PEDOT and Mn-Ni-Ru oxide/PEDOT electrodes used in an electro-osmotic pump (EOP) have shown better efficiency compared to Mn-Ni oxide and Mn-Ni oxide/PANI electrodes through testing in water as a pumping solution. EOP using a Mn-Ni-Ru oxide/PEDOT electrode was also tested in a 0.5 mM $Li_2SO_4$ solution as a pumping solution to confirm the effect of the $Li^+$ insertion/de-insertion reaction of Ruthenium oxide on the EOP. Experimental results show that the flow rate increases with the increase in current in a 0.5 mM $Li_2SO_4$ solution compared to that obtained when water was used as a pumping solution.

• 한국전기화학회:학술대회논문집
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• 한국전기화학회 2005년도 춘계총회 및 학술발표회
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• pp.52-52
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• 2005