• Bulletin of the Korean Chemical Society
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• v.34 no.9
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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 %.

• Proceedings of the KIEE Conference
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• 2004.07c
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• pp.1740-1742
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• 2004

산소 과전압이 낮은 $MnO_2$를 촉매로 사용하여 반도체 산화물계의 산소선택성 전극을 제조하고 산화물 코팅층의 미세구조와 전기화학적 특성을 분석하였다. Ti 기판에 열분해 법을 이용하여 $MnO_2$ 피막을 형성하였고, 또한 binder를 이용한 코팅 방법을 이용하여 Ti, Fb 기판에 $MnO_2$ 피막층을 형성하였다. 450$^{\circ}C$에서 1시간 열분해하여 약 1 ${\mu}m$의 $MnO_2$ 피막층을 형성 시켰으나 Ti 기판과의 접착력이 약하여 피막자체에 대한 전기화학적 특성은 관찰할 수 없었다. PVDF : $MnO_2$의 함량비가 1:1에서 1:6 까지는 DMF의 함량에 무관하게 전극 특성이 나타나지 않았지만 20:1 이상의 조성에서는 균일한 C-V 특성을 나타냈고, 산소 발생 과전압도 약 1.4V 정도로 감소되었다. 그러나 Ti 기판의 경우 열분해법을 이용하여 제조된 전극과 같이 낮은 기판과의 접착력 때문에 $MnO_2$ 피막층의 촉매효과가 현저하게 감소하였다.

• Journal of the Korean Electrochemical Society
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• v.3 no.4
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• pp.235-240
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• 2000

Screen-printing and doctor blade method were investigated and proposed as an electrode coating process for high power capacitor. CV measured from the amorphous $MnO_2$ electrode prepared by screen-printing shows closer to ideal capacitor characteristics. Specific capacitances calculated from CVs with potential scan rate of 50mV/s were 5.8, 81.8, and 172.0 F/g for electrode thickness of $140{\mu}m,\;24{\mu}m,\; 3{\mu}m$, respectively. Assumed that utilization of active $MnO_2$ in electrode of screen-printing is $100\%$, those were $3.4\%$ in one of paste method and $47.6\%$ in one of doctor blade method. The screen-printing can be good technique to coat thin film on current collector for high power application.

• Journal of the Korean Vacuum Society
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• v.15 no.5
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• pp.527-533
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• 2006

Spinel $LiNi_xMn_{2-x}O_4$ thin films were synthesized up to x = 0.9 by a sol-gel method employing spin-coating. The Ni-substituted films were found to maintain cubic structure at low x but to exhibit tetragonal structure for $x{\geq}0.6$. Such cubic-tetragonal phase transition indicates that $Ni^{3+}(d7)$ ions with low-spin $(t_{2g}^6,e_g^1)$ state occupy the octahedral sites of the compound, thus being subject to the Jahn-Teller distortion. By x-ray photoelectron spectroscopy both $Ni^{2+}$ and $Ni^{3+}$ ions were detected. Optical properties of the $LiNi_xMn_{2-x}O_4$ films were investigated by spectroscopic ellipsometry (SE) in the visible?ultraviolet range. The measured dielectric function spectra by SE mainly consist of broad absorption structures attributed to charge-transfer (CT) transitions, $O^{2-}(2p){\rightarrow}Mn^{4+}(3d)$ for 1.9 $(t_{2g})$ and $2.8{\sim}3.0$ eV $(e_g)$ structures and $O^{2-}(2p){\rightarrow}Mn^{3+}(3d)$ for 2.3 $(t_{2g})$ and $3.4{\sim}3.6$ eV $(e_g)$ structures. Also, sharp absorption structures were observed at about 1.6, 1.7, and 1.9 eV, interpreted as due to d-d crystal-field transitions within the octahedral $Mn^{3+}$ ion. The strengths of these absorption structures are reduced by the Ni substitution. Rapid reduction of the CT transition strength involving the eg states for x = 0.6 is attributed to the reduced wavefunction overlap between the $e_g$ and the $O^{2-}(2p)$ states due to the tetragonal extension of the lattice constant by the Jahn-Teller effect.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2002.11a
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• pp.313-316
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• 2002

비철금속 습식 제련용 고효율 장수명의 양극을 개발하기 위해서 산소 과전압이 낮은 $MnO_{2}$를 촉매로 사용하여 반도체 산화물계의 산소선택성 전극을 제조하고 산화물 coating층의 미세구조와 전기화학적 특성을 분석하였다. PVDF : $MnO_{2}$의 함량비플 1 : 1 에서 1 : 40까지 정량적으로 변화시켰고， 용제의 점도에 지배적인 영향을 미치는 DMF의 함량을 각각의 고정된 PVDF : $MnO_{2}$의 함량비에서 변화시켜 용제를 제조하였으며 4% $HNO_{3}$ 용액에 세척된 Pb전극을 1.5 mm/sec 의 속도로 5회 dipping 하였다. PVDF : $MnO_{2}$ = 1 : 6인 경우 PVDF의 양이 증가하고 DMF의 양이 감소할수록 피막층이 두꺼워지고 PVDF : DMF = 4 : 96인 경우 pb 전극의 피막층이 얇기 때문에 박리현상이 일어났으며 이는 산화물 용제의 낮은 점도 때문인 것으로 판단된다. 또한 PVDF : DMF = 10 : 90의 경우는 5회 dipping 하여 약 $150{\mu}m$의 피막층을 형성하였다. PVDF : Mn02의 함량비가 1:1에서 1:6 까지는 DMF의 함량에 무관하게 전극 특성이 나타나지 않았지만 $MnO_{2}$의 양이 상대적으로 증가하면 cycle 이 증가하더라도 거의 일정한 전류 값을 갖고$MnO_2$와 PVDF의 비가 20:1 이상의 조성에서는 균일한 CV 특성을 나타냈다 이는 $MnO_{2}$가 효과적으로 촉매 작용을 한 것으로 판단되며 anodic polarization에 의한 산소 발생 과전압도 약 1.4V 정도로 감소되었다.

• Bulletin of the Korean Chemical Society
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• v.35 no.5
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• pp.1516-1522
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• 2014

A series of 20 wt % $(NH_4)_2SO_4$ and 3 wt % $Al_2O_3$ surface treatments were applied to $Li[Li_{0.2}Mn_{0.54}Co_{0.13}Ni_{0.13}]O_2$ substrates. The $Li[Li_{0.2}Mn_{0.54}Co_{0.13}Ni_{0.13}]O_2$ substrates were synthesized using a co-precipitation method. Sample (a) was left pristine and variations of the 20 wt % $(NH_4)_2SO_4$ and 3 wt % $Al_2O_3$ were applied to samples (b), (c) and (d). XRD was used to verify the space group of the samples as R$\bar{3}$m. Additional morphology and particle size data were obtained using SEM imagery. The $Al_2O_3$ coating layers of sample (b) and (d) were confirmed by TEM images and EDS mapping of the SEM images. 2032-type coin cells were fabricated in a glove box in order to investigate their electrochemical properties. The cells were charged and discharged at room temperature ($25^{\circ}C$) between 2.0V and 4.8V during the first cycle. The cells were then charged and discharged between 2.0V and 4.6V in subsequent cycles. Sample (d) exhibited lower irreversible capacity loss (ICL) in the first charge-discharge cycle as compared to sample (c). Sample (d) also had a higher discharge capacity of ~250 mAh/g during the first and second charge-discharge cycles when compared with sample (c). The rate capability of the $Al_2O_3$-coated sample (b) and (d) was lower when compared with sample (a) and (c). Sample (d), coated with $Al_2O_3$ after the surface treatment with $(NH_4)_2SO_4$, showed an improvement in cycle performance as well as an enhancement of discharge capacity. The thermal stability of sample (d) was higher than that of the sample (c) as the result of DSC.

• Journal of Electrochemical Science and Technology
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• v.7 no.2
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• pp.179-184
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• 2016

The interface between the surface of a cathode material and the electrolyte gives rise to surface reactions such as solid electrolyte interface (SEI) and chemical side reactions. These reactions lead to increased surface resistance and charge transfer resistance. It is consequently necessary to improve the electrochemical characteristics by suppressing these reactions. In order to suppress unnecessary surface reactions, we coated cathode material using polypropylene (PP). The PP coating layer effectively reduced the SEI film that is generated after a 4.3 V initial charging process. By mitigating the formation of the SEI film, the PP-coated Li[(Ni_0.6Co_0.1Mn_0.3)_0.36(Ni_0.80Co_0.15Al0.05)_0.64)]O₂(NCS) electrode provided enhanced transport of Li⁺ ions due to reduced SEI resistance (R_SEI) and charge transfer resistance (R_ct). The initial charge and discharge efficiency of the PP-coated NCS electrode was 96.2 % at a current density of 17 mA/g in a voltage range of 3.0 ~ 4.3 V, whereas the efficiency of the NCS electrode was only 94.7 %. The presence of the protective PP layer on the cathode improved the thermal stability by reducing the generated heat, and this was confirmed via DSC analysis by an increased exothermic peak.

• Proceedings of the Korean Institute of Surface Engineering Conference
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• 2018.06a
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• pp.75-75
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• 2018

Commercially pure titanium (CP-Ti) and Ti-6Al-4V alloys have been widely used in implant materials such as dental and orthopedic implants due to their corrosion resistance, biocompatibility, and good mechanical properties. However, surface modification of titanium and titanium alloys is necessary to improve osseointegration between implant surface and bone. Especially, when titanium oxide nanotubes are formed on the surface of titanium alloy, cell adhesion is greatly improved. In addition, plasma electrolytic oxide (PEO) coatings have a good safety for osseointegration and can easily and quickly form coatings of uniform thickness with various pore sizes. Recently, the effects of bone element such as magnesium, zinc, strontium, silicon, and manganese for bone regeneration are researching in dental implant field. The purpose of this study was researched on the surface morphology of PEO-treated Ti-6Al-4V alloy after anodic titanium oxide treatmentusing various instruments. Ti-6Al-4V ELI disks were used as specimens for nanotube formation and PEO-treatment. The solution for the nanotube formation experiment was 1 M $H_3PO_4$ + 0.8 wt. % NaF electrolyte was used. The applied potential was 30V for 1 hours. The PEO treatment was performed after removing the nanotubes by ultrasonics for 10 minutes. The PEO treatment after removal of the nanotubes was carried out in the $Ca(CH_3)_2{\cdot}H_2O+(CH_3COO)_2Mg{\cdot}4H_2O+Mn(CH_3COO)_2{\cdot}4H_2O+Zn(CH_3CO_2)_2Zn{\cdot}2H_2O+Sr(CH_2COO)_2{\cdot}0.5H_2O+C_3H_7CaO_6P$ and $Na_2SiO_3{\cdot}9H_2O$ electrolytes. And the PEO-treatment time and potential were 3 minutes at 280V. The morphology changes of the coatings on Ti-6Al-4V alloy surface were observed using FE-SEM, EDS, XRD, AFM, and scratch tester. The morphology of PEO-treated surface in 5 ion coating solution after nanotube removal showed formation or nano-sized mesh and micro-sized pores.

• Corrosion Science and Technology
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• v.17 no.3
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• pp.91-100
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• 2018

Development of biodegradable implants for treatment of complex bone fractures has recently become one of the priority areas in biomedical materials research. Multifunctional corrosion resistant and bioactive coatings containing hydroxyapatite $Ca_{10}(PO_4)_6(OH)_2$ and magnesium oxide MgO were obtained on Mg-Mn-Ce magnesium alloy by plasma electrolytic oxidation. The phase and elemental composition, morphology, and anticorrosion properties of the coatings were investigated by scanning electron microscopy, energy dispersive spectroscopy, potentiodynamic polarization, and electrochemical impedance spectroscopy. The PEO-layers were post-treated using superdispersed polytetrafluoroethylene powder. The duplex treatment considerably reduced the corrosion rate (>4 orders of magnitude) of the magnesium alloy. The use of composite coatings in inducing bioactivity and controlling the corrosion degradation of resorbable Mg implants are considered promising. We also applied the plasma electrolytic oxidation method for the formation of the composite bioinert coatings on the titanium nickelide surface in order to improve its electrochemical properties and to change the morphological structure. It was shown that formed coatings significantly reduced the quantity of nickel ions released into the organism.

• Journal of the Korean Electrochemical Society
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• v.7 no.2
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• pp.94-99
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• 2004

Anode-supported flat tubular solid oxide fuel cell (SOFC) was investigated to increase the cell power density. The anode-supported flat tube was fabricated by extrusion process. The porosity and pore size of Ni/YSZ ($8mol\%$ yttria-stabilized zirconia) cermet anode were $50.6\%\;and\;0.23{\mu}m$, respectively. The Ni particles in the anode were distributed uniformly and connected well to each other particles in the cermet anode. YSZ electrolyte layer and multilayered cathode composed of $LSM(La_{0.85}Sr_{0.15})_{0.9}MnO_3)/YSZ$ composite, LSM, and $LSCF(La_{0.6}Sr_{0.4}Co_{0.2}Fe_{0.7}O_3)$ were coated onto the anode substrate by slurry dip coating, subsequently. The anode-supported flat tubular cell showed a performance of $300mW/cm^2 (0.6V,\; 500 mA/cm^2)\;at\;500^{\circ}C$. The electrochemical characteristics of the flat tubular cell were examined by ac impedance method and the humidified fuel enhanced the cell performance. Areal specific resistance of the LSM-coated SUS430 by slurry dipping process as metallic interconnect was $148m{\Omega}cm^2\;at\;750^{\circ}C$ and then decreased to $148m{\Omega}cm^2$ after 450hr. On the other hand, the LSM-coated Fecralloy by slurry dipping process showed a high area specific resistance.