• Title/Summary/Keyword: 구조 전해질

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헵타메틴 시아닌색소의 전기화학적 특성 분석

  • Kim, Yeong-Seong;Sin, Jong-Il;Park, Su-Yeol;Jeon, Geun;Son, Yeong-A
    • Proceedings of the Korean Society of Dyers and Finishers Conference
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    • 2009.11a
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    • pp.21-22
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    • 2009
  • 최근, 헵타메틴 시아닌색소(heptamethinecyanine)는 그 적용 범위가 넓기 때문에 많은 연구자들의 관심을 받고 있다. 특히, photo-sensitizers, dye lasers, optical recordings와 storage media 등 다양한 분야에 적용이 가능하다. 헵타메틴 시아닌색소의 주된 특징은 polymethine 사슬에 연결된 cyclohexene 고리에 의하여 근적외선 부근에서 흡수가 이뤄진다는 것이다. 근적외선 색소의 흡수 특성을 HOMO와 LUMO 에너지 전위를 사용하여, 수치화 함으로써 분자간, 분자내 상호작용을 분석 할 수 있다. 따라서, 본 실험은 헵타메틴 시아닌 색소의 치환체에 따른 전기화학적 특성을 순환 전압-전류법(Cyclic voltammetry)과 분자 모델링을 통하여 HOMO와 LUMO의 에너지 준위를 구하고, 치환체 효과가 헵타메틴 시아닌색소에 미치는 전기화학적 특성을 UV-Vis와 계산으로부터 얻어진 에너지준위를 분석하고자 한다. 본 실험에 사용된 Uv-Vis 스펙트럼 측정은 Agilent 8453 UV-Vis spectrophotometer를 사용하였고, 전기화학적 분석 방법인 순환 전압-전류법은 Versa STAT 3 (Princeton allied research in USA)를 사용하였다. 순환전압-전류법의 측정은 Acetonitrile 용액에 $TBAPF_6$ (Tetrabutylammonium hexafluorophosphate)를 전해질로 하고, Ag/$Ag^+$을 기준전극으로 사용하여 주사 속도를 50mV/s로 하여 측정 하였다. 치환체에 의한 영향을 알아보기 위하여 분자구조 최적화 모델링을 사용하였다. 3차원 분자입체 특성 및 에너지 준위 상태는 Materials studio 4.2를 사용하여 특성을 예측 하였다. 본 연구에서는, 헵타메틴 시아닌 색소의 기본 골격에 각기 다른 치환체를 치환 시켜 치환체에 의한 영향을 전기화학적인 방법인 순환 전압-전류법(Cyclic voltammetry)와 분자 모델링 방법을 사용하여, HOMO와 LUMO에너지 준위 값을 구함으로써 치환체에 의한 영향을 알아보았다. 치환체로는 Dye 1과 Dye 2로 치환된 헵타메틴 시아닌 색소를 사용하였다. 이렇게 얻어진 HOMO/LUMO 에너지 준위 값으로부터 이온화 에너지($I_p$)와 전자 친화도($E_a$) 또한 구할 수 있는데, $I_p$$E_a$는 분자 오비탈과 전자전이에 관련된 값들이고, 이는 계산을 통하여 얻을 수 있다. 순환 전압-전류법의 계산 방법은 봉우리 전위(peak postential)와 (onset potential)방법이 있는데, 이 계산을 통한 전위 값들이 봉우리 전위 계산 방법이 onset potential 방법에 비하여 작은 전위 값으로 나타난다. 하지만 이 두 가지 방법 모두 현재 순환 전압-전류법을 사용하여 HOMO/LUMO 에너지 준위를 측정하는 방법에 쓰이고 있으며, 어떠한 계산 방법이 더 정확하다고는 말 할 수 없지만, 본 실험 결과를 통하여 비교 분석한 결과 onset potential 계산 방법이 봉우리 전위 계산 방법에 비하여 정확하다고 판단된다. Dye 1과 Dye 2를 순환 전압-전류법으로 측정한 결과 각기 다른 전위를 나타내고 이것을 계산을 통하여 정량화하면 Dye 2가 Dye 1에 비하여 높은 전위 값을 갖음을 알 수 있는데, 이것은 ethyl 에 비하여 surful 원자의 전자공여성이 더 크다고 할 수 있다.

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The fabrication and sensing characteristics of conducting polymer sensors for Measurement of VOCs (Volatile organic compounds) gas (휘발성 유기 화합물 가스 측정을 위한 전도성 고분자 센서의 제조(製造) 및 감응(感應) 특성(特性))

  • Paik, J.H.;Hwang, H.R.;Roh, J.G.;Huh, J.S.;Lee, D.D.;Lim, J.O.;Byun, H.G.
    • Journal of Sensor Science and Technology
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    • v.10 no.2
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    • pp.125-133
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    • 2001
  • Conducting polymer sensors show high sensitivity when exposed to volatile organic compounds gases at room temperature. The 8 sensor array using by polypyrrole and polyaniline has been fabricated by chemical polymerization for measuring sensing characteristics of VOCs gases. Conducting polymer was polymerized by using distilled pyrrole, aniline as a monomer and ammonium persulfate (APS) as an oxidant and dodecylbenzene sulfonic acid (DBSA) as a dopant. Dedoped film was synthesized by reverse voltage and redoped film was synthesized by using 1-octanesulfonic acid sodium salt as another dopant in electrochemical cell. The sensitivity and reversibility were influenced by doping, dedoping, redoping and thickness for the polypyrrole and polyaniline. We investigated the relation between the structure of conducting polymer and sensitivity of these sensors through the analysis of scanning electron microscope (SEM), scanning probe microscope (SPM) and $\alpha$-step.

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Effect of Electrolyte Amounts on Electrochemical Properties of Coin-Type Lithium-Ion Cells (액체전해액의 함량에 따른 리튬이온전지 코인셀의 전기화학적 특성 연구)

  • Yoon, Byeolhee;Han, Taeyeong;Kim, Seokwoo;Jin, Dahee;Lee, Yong min;Ryou, Myung-Hyun
    • Journal of the Korean Electrochemical Society
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    • v.21 no.2
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    • pp.39-46
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    • 2018
  • Many studies on the electrochemical performance of Li secondary batteries have been obtained using coin-type cells due to the ease of assembly, low cost and ensuring reproducibility. The coin-type cell consists of a case, a gasket, a spacer disk, and a wave spring. These structural features require a greater amount of liquid electrolyte to assemble than other types of cells such as laminated cells and cylindrical cells. Nevertheless, little research has been conducted on the effect of excess liquid electrolytes on the electrochemical performances of Li secondary batteries. In this study, we investigate the effect of different amounts of electrolyte on the coin-type cells. The amount of electrolytes is adjusted to 30 and $100mg\;mAh^{-1}$. Cycle performances at room temperature ($25^{\circ}C$) and high temperature ($60^{\circ}C$) and high voltage are performed to investigate the electrochemical properties of the different amount of electrolytes. In the case of the unit cell including the electrolyte of $30mg\;mAh^{-1}$, the discharging capacity retention characteristic is excellent in comparison with the case of $100mg\;mAh^{-1}$ under the high temperature and high voltage condition. The former shows a larger increase in internal resistance than the latter, confirming that the amount of electrolyte significantly influences the discharge capacity retention characteristics of the battery.

Improvement of Oxidative Stability for Non-fluorinated Membranes Prepared by Substituted Styrene Monomers (스티렌 유도체를 이용한 비불소계 고분자 전해질막의 산화적 안정성 개선)

  • Moon, Seung-Hyeon;Woo, Jung-Je;Fu, Rong-Qiang;Seo, Seok-Jun;Yun, Sung-Hyun
    • Membrane Journal
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    • v.17 no.4
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    • pp.294-301
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    • 2007
  • To improve oxidative stability of non-fluorinated styrene-based polymer electrolyte membranes, copolymerized membranes were prepared using styrene derivatives such as p-methylstyrene, t-butylstyrene, and ${\alpha}-methylstyrene$ by monomer sorption method. Prepared membrane was characterized by measurement of weight gain ratio, water content, ion-exchange capacity, proton conductivity, and oxidative stability under the accelerated condition. It was found that each step of monomer sorption method including sorption, polymerization and sulfonation could be affected by the properties and the structures of styrenederivatives. Due to difficulty of polymerization, ${\alpha}$-methylstyrene was copolymerized with styrene or p-methylstyrene. Prepared membrane using ${\alpha}-methylstyrene$ and styrene showed higher performance and stability comparing to copolymerized membrane with styrene. However, copolymerized membranes with ${\alpha}-methylstyrene$ did not showed much improved oxidative stability comparing to styrene membrane due to their lower molecular weight. The t-butylstyrene membrane showed a low performance due to substituted bulky-butyl group which prevents sorption and sulfonation reaction. However, copolymerized t-butylstyrene membranes with p-methylstyrene showed good performance and much improved stability than the styrene membranes.

Preparation and Characterization of Proton Conducting Crosslinked Membranes Using Polymer Blends (폴리머 블렌딩을 이용한 수소 전도성 가교형 막의 제조와 그 특성)

  • Kim, Jong-Hak;Lee, Do-Kyoung;Choi, Jin-Kyu;Seo, Jin-Ah;Roh, Dong-Kyu
    • Membrane Journal
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    • v.17 no.4
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    • pp.311-317
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    • 2007
  • Proton conducting crosslinked membranes have been prepared by polymer blending, which consist of poly(vinyl alcohol-co-ethylene) (PVA-co-PE) and poly(styrene sulfonic acid-co-maleic acid) (PSSA-co-PMA) at 50 : 50 wt ratio. Two kinds of PSSA-co-PMA copolymer with 3 : 1 and 1 : 1 the molar ratio of PSSA to PMA wereused as a proton conducting source. The ethylene content of PVA-co-PE was also changed as 0, 27 and 44 mol%. The membranes were thermally crosslinked via the esterification reaction between -OH of PVA and -COOH of PMA, as demonstrated by FT-IR spectroscopy (PVA-co-PE)/(PSSA-co-PMA) membranes with 3 : 1 the molar ratio of PSSA to PMA showed higher ion exchange capacity (IEC), lower water uptake and higher proton conductivity than those with 1 : 1 molar ratio. As the PE concentration increased, the IEC values, water uptake and proton conductivities decreased continuously. These properties were elucidated in terms of competitive effect between the concentration of sulfonic acid, hydrophilicity and the crosslinked structure of membranes.

A Study on Sulfonated Fluorenyl Poly(ether sulfone)s as Catalyst Binders for Polymer Electrolyte Fuel Cells (고분자 전해질 연료전지 촉매층 바인더를 위한 Sulfonated Fluorenyl Poly(ether sulfone)에 관한 연구)

  • Cho, Won Jae;Lee, Mi Soon;Lee, Youn Sik;Yoon, Young Gi;Choi, Young Woo
    • Journal of the Korean Electrochemical Society
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    • v.19 no.2
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    • pp.39-44
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    • 2016
  • Oxygen reduction reaction in the fuel cell (ORR) plays a dominant role in the overall reaction. In addition, the low compatibility between the membrane and the binder consisted of different materials, greatly reduces the efficiency of the fuel cell performance. In view of these two problems, geometrically modified copolymers with 9.9_Bis (4-hydroxyphenyl) were synthesized via condensation reaction instead of conventional biphenol and were adopted as hydrocarbon ionomer binders. By utilizing these binders, two kinds of MEAs using fluorinated Nafion membrane and hydrocarbon based membrane were manufactured in order to electrochemical performance evaluation. With current-voltage curves, there was no significant difference in the 0.6 V when two types of membrane were applied. Also, tafel slope became considerably lower as compared to the Nafion membrane. Thus, it is determined that the new hydrocarbon binder is expected to contribute the improvement in performance of fuel cells.

The Effect of Calcination Temperature on the Layered Li1.05Ni0.9Co0.05Ti0.05O2 for Lithium-ion Battery (리튬이온전지용 층상 Li1.05Ni0.9Co0.05Ti0.05O2에 대한 소성 온도의 영향)

  • Ko, Hyoung Shin;Park, Hyun Woo;Lee, Jong Dae
    • Korean Chemical Engineering Research
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    • v.56 no.5
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    • pp.718-724
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    • 2018
  • In this study, the $Ni_{0.9}Co_{0.05}Ti_{0.05}(OH)_2$ precursor was prepared by the concentration gradient co-precipitation method. In order to overcome the structural change due to oxygen desorption in the cathode active material with high nickel content, the physical and electrochemical analysis of the cathode active material according to the calcination temperature were investigated. Physical properties of $Li_{1.05}Ni_{0.9}Co_{0.05}Ti_{0.05}O_2$ were analyzed by FE-SEM, XRD and TGA. The electrochemical performance of the coin cell using a cathode active material and $LiPF_6$(EC:EMC=1:2 vol%) electrolyte was evaluated by the initial charge/discharge efficiency, cycle retention, and rate capabilities. As a result, the initial capacity and initial efficiency of cathode materials were excellent with 244.5~247.9 mAh/g and 84.2~85.8% at the calcination temperature range of $750{\sim}760^{\circ}C$. Also, the capacity retention exhibited high stability of 97.8~99.1% after 50cycles.

Fabrication of TiO2/polyelectrolyte thin film for a methyl mercaptan gas sensor (메칠멜캅탄 가스센서용 TiO2/전해질폴리머 박막 제조)

  • Kim, Jin-Ho;Hwang, Jong-Hee;Lee, Mi-Jai;Kim, Sei-Ki;Lim, Tae-Young
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.20 no.5
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    • pp.221-226
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    • 2010
  • Quartz crystal microbalance (QCM) gas sensor to detect methyl mercaptan ($CH_3SH$) gas was fabricated by depositing $TiO_2$ nanoparticles and polyelectrolyte on the electrode of QCM. The $TiO_2$/poly(sodium 4-styrenesulfonate) (PSS) thin film fabricated by a layer-by-layer self-assembly (LBL-SA) method showed a high surface area and increased the sensitivity of gas sensor. When the QCM sensors coated with triethanolamine (TEA) or ($TiO_2$/PSS) were exposed to methyl mercaptan gas (1.0 ppm), the frequency shifts of QCM with TEA casting film and $TiO_2$/PSS thin film were ca. 9 Hz and ca. 24 Hz, respectively. As the bilayer number of ($TiO_2$/PSS) increased, the frequency shift of QCM sensor with ($TiO_2$/PSS) thin film was gradually increased. In addition, the frequency shift of QCM sensor was gradually increased as the concentration of methyl mercaptan gas increased from 0.5 ppm to 2.0 ppm. In this study, the surface morphology and sensor property of QCM sensor coated with ($TiO_2$/PSS) thin film were measured.

Electrochemical Behavior and Morphology of Anodic Titanium Oxide Films (양극산화에 의한 티타늄 산화피막의 전기화학적 거동과 형상)

  • Byeon K.J.;Kim C.S.;Zhu Xiaolong;Kim K.H.
    • Journal of Biomedical Engineering Research
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    • v.21 no.3 s.61
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    • pp.273-277
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    • 2000
  • The galvanostatic anodization of commercially Pure titanium plate (c.p.Ti, grade 2) was investigated in various concentrations of aqueous $H_3PO_4$ from 0.05M to 0.7M. The surfaces of anodic oxide films, formed by the current density in the range between 0.3 and $l.0 A/dm^2$. were analyzed by SEM and XRD. The voltage-time (V-T) curves displayed an initial linear part and a subsequent parabolic part, and the initial slopes increased with an increase in the current density in 0.05M $H_3PO_4$. As the concentration of the electrolyte increased, the V-T corves exhibit no change but the final voltage decreased. The anodic oxide film of titanium developed from fine grains to snowflake-like grains in a layered structure with an increase in the concentration of the electrolyte and current density. Sparking at the interface of the oxide/electrolyte accompanied the local deposition and dissolution of the oxide film through discharging. The crystallinity of the anodic oxide film increased with the anodizing voltage and decreased with an increase in the concentration of the electrolyte.

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Synthesis of Pt-Bi/Carbon Electrodes by Reduction Method for Direct Methanol Fuel Cell (환원법에 의한 직접 메탄올 연료전지(DMFC)용 Pt-Bi/Carbon 전극제조)

  • Kim, Kwan Sung;Kim, Min Kyung;Noh, Dong Kyun;Tak, Yongsug;Baeck, Sung-Hyeon
    • Applied Chemistry for Engineering
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    • v.22 no.5
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    • pp.479-485
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    • 2011
  • Pt-Bi/C catalysts supported on carbon black with various Pt/Bi ratios were synthesized by a reduction method. Chloroplatinic acid hydrate ($H_2PtCl_6{\cdot}xH_2O$) and bismuth (III) nitrate pentahydrate ($Bi(NO_3)_3{\cdot}5H_2O$) were used as precursors for Pt and Bi, respectively. Before loading metal on carbon, heat treatment and pretreatment of carbon black in an acidic solution was conducted to enhance the degree of dispersion. The physical property of the synthesized catalysts was investigated by X-ray diffraction and X-ray photoelectron spectroscopy. The XRD pattern of untreated Pt-Bi/C catalyst showed BiPt and $Bi_2Pt$ peaks in addition to Pt peaks. These results imply that Bi atoms were incorporated into the Pt crystal lattice by Pt-Bi alloy formation. The catalytic activity for methanol oxidation was measured using cyclic voltammetry in a mixture of 0.5 M $H_2SO_4$ and 0.5 M $CH_3OH$ aqueous solution. The addition of proper amount of Bi was found to significantly improve catalytic activity for methanol oxidation. The catalytic activity for methanol oxidation was closely related to the stability between electrode and electrolyte. In order to investigate the stability of catalysts, chronoamperometry analysis was carried out in the same solution at 0.6 V.