• Journal of the Korean Electrochemical Society
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• v.19 no.1
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• pp.21-27
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• 2016

Vanadium redox flow batteries (VRFBs) using the electrolytes containing various vanadium ions in sulfuric acid as supporting solution are one of the energy storage devices in alternatively charging and discharging operation modes. The positive electrolyte contains $V^{5+}/V^{4+}$ and the negative electrolyte $V^{2+}/V^{3+}$ depending on the operation mode. To prevent the mixing of two solutions, proton exchange membranes are mainly used in VRFBs. Nafion 117 could be the most promising candidate due to the strong oxidative property of $V^{5+}$ ion, but causes high crossover of electroactive species to result in a decrease in coulombic efficiency. In this study, the composite membranes using Nafion ionomer and porous polyethylene substrate were prepared to keep good chemical stability and to decrease the cost of membranes, and were compared to the properties and performance of the commercially available electrolyte membrane, Nafion 117. As a result, the water uptake and ionic conductivity of the composite membranes increased as the thickness of the composite membranes increased, but those of Nafion 117 slightly decreased. The permeability of vanadium ions for the composite membranes significantly decreased compared to that for Nafion 117. In a single cell test for the composite membranes, the voltage efficiency decreased and the coulombic efficiency increased, finally resulting in the similar energy efficiency. In conclusion, the less cost of the composite membranes by decreasing 6.4 wt.% of the amount of perfluorinated sulfonic acid polymer due to the introduction of porous substrate and lower vanadium ion permeability to decrease self-discharge were achieved than Nafion 117.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.9 no.6
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• pp.590-596
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• 1999

The effects of additives on the Zn electrodeposition in chloride-based electrolyte were investigated using circulation cell with three electrodes system. The cathodic polarization increased with the addition of polyethylenglycol (hereafter PEG) in electrolyte. This was attributed to the adsorption of the additives on the electrode and the inhibition of migration of metal ion. The PEG, however, did not have any noticeable effect on the properties of plating solutions at the concentration used. The effect of PEG on the electrocrystallization was related to its molecular weight. With the increase of molecular weight, the cathodic polarization increased, while the surface roughness was improved with the decrease of brightness. Especially, the PEG mixed with different molecular weights was the most effective. The orientation and the type of the deposited grains were changed and refined by PEG, which resulted in the modification of deposited surface roughness and brightness.

• 한국신재생에너지학회:학술대회논문집
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• 2005.06a
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• pp.281-283
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• 2005

Water management in polymer electrolyte membrane fuel cells(PEMFCs) is one of the most challenging issues. Freeze start-up in the automotive applications is also important research topic in the PEMFC field. Transportation of proton and separation of reactant gases are main roles of polymer electrolyte membranes. It has been known that water in the membrane conducts as a vehicle for the proton transportation. At sub-zero temperature, the frozen water blocks the access of reactant gases to the active sites of electrode as well as occurs the physical destruction of fuel cell structures. In this study, property changes of electrolyte membranes in the freeze conditions $(at\;-25^{\circ}C)$ were investigated. For the various amount of water contained membranes, the property changes, especially for the proton conductivity, were observed after several times of freeze/thaw$(-25\~80^{\circ}C)$ cycle.

• 한국신재생에너지학회:학술대회논문집
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• 2009.06a
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• pp.270-273
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• 2009

A comb-like copolymer consisting of a poly(vinylidene fluoride-co-chlorotrifluoro-ethylene) backbone and poly(hydroxy ethyl acrylate) side chains, i.e. P(VDF-co-CTFE)-g-PHEA, was synthesized through atom transfer radical polymerization (ATRP) using CTFE units as a macroinitiator. Successful synthesis and a microphase-separated structure of the copolymer were confirmed by proton nuclear magnetic resonance (1H-NMR), FT-IR spectroscopy, and transmission electron microscopy (TEM). This comb-like polymer was crosslinked with 4,5-imidazole dicarboxylic acid (IDA) via the esterification of the -OH groups of PHEA and the -COOH groups of IDA. Upon doping with phosphoric acid ($H_3PO_4$) to form imidazole-$H_3PO_4$ complexes, the proton conductivity of the membranes continuously increased with increasing $H_3PO_4$ content. A maximum proton conductivity of 0.015 S/cm was achieved at $120^{\circ}C$ under anhydrous conditions. In addition, these P(VDF-co-CTFE)-g-PHEA/IDA/$H_3PO_4$ membranes exhibited good mechanical properties (765 MPa of Young's modulus), and high thermal stability up to $250^{\circ}C$, as determined by a universal testing machine (UTM) and thermal gravimetric analysis (TGA), respectively.

• 한국신재생에너지학회:학술대회논문집
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• 2006.11a
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• pp.421-424
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• 2006

Nafion/Pt/Polypyrrole composite membranes were fabricated by chemical in-situ polymerization of pyrrole monomers with Pt precursors in Nafion matrix for DMFC. We demonstrated that positively charged pyrrolinum groups of polypyrrole particles were co-interacted with sulfonic groups of Nafion as verified by FT-IR results. Mutual interaction between $Nafion-SO_3^-$ (or negatively charged Pt precursors) and Polypyrrole$-NH_2^+$ influenced the physical properties of pristine Nafion. Thermal property proton conductivity, methanol permeability, and cell performance of pristine and modified Nafion were analyzed for an application of DMFC membrane. Thermal stabilities of sulfonic groups and side chains in Nafion/Pt/polypyrrole composite membranes were higher than those of Nafion due to mutual interaction between sulfonic groups of Nafion and pyrrolinum groups of polypyrrole. Methanol permeabilities of Nafion/Pt/Polypyrrole composite were reduced more proton conductivities with the increase in the content of Pt particles. As a result of that, the enhancement of cell performance by Nafion/Pt/Polypyrole O2 relative to Nafion was more pronounced under the specific experimental condition such as high temperature and more concentrated methanol solution.

• Journal of the Korean Chemical Society
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• v.27 no.1
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• pp.1-8
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• 1983

Solvent effects on nucleophilic substitution reaction of naphthalene sulfonyl chlorides with pyridine in protic and aprotic solvent have been studied by means of conductometry. Results showed that the rate constants increased with dielectric constants for protic solvents, while they decreased with dielectric constants for aprotic solvents, except for acetonitrile which has a higher dielectric constant but had also greater rate constant. The rate constants were shown to be more susceptible to polarity-polarizability parameter, , than to hydrogen bond donor acidity parameter, ${\alpha}$, indicating that the pulling effect of hydrogen bonding solvent.

• Membrane Journal
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• v.20 no.3
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• pp.173-184
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• 2010

Microbial fuel cell (MFC) is a promising renewable energy source that can generate electrical energy from organic wastes using microbe. This technology has been regarded as a future green alternative energy in that MFC makes use of organic-rich wastewater and also reduces waste sludges as well as produces electricity. To be practically realized, however, achieving higher power density than now is demanded, which may be possible by eliminating various negative factors to act as resistances in MFC operations. For instance, highly activated microbes, highly conductive electrode materials, and fast electron transfer between microbes and electrodes can lead to MFC with high power density. In particular, polymer electrolyte membranes are also a key component for improved MFC performance.

• Korean Chemical Engineering Research
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• v.45 no.4
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• pp.391-395
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• 2007

A new electrode binder mixed with sulfonated poly (ether ether ketone) (sPEEK) and Nafion is prepared and investigated as an anode binder for direct methanol fuel cell (DMFC). The mixed binder (95 wt% sPEEK/5 wt% Nafion) shows high proton conductivity and methanol transport rate as well as no dissolution and brittleness. The effect of content as an anode binder on the performance of the cell with the given cathode is investigated. The unit cell with the anode containing 10wt% mixed binder showed the highest cell performance.

• 한국신재생에너지학회:학술대회논문집
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• 2011.05a
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• pp.97.1-97.1
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• 2011

저온에서 양이온 고분자막을 사용하는 고분자 연료전지의 경우 뛰어난 성능과 다양한 응용분야로 인해 많은 연구와 실증이 이루어지고 있지만 공기극에서의 느린 산소 환원반응으로 인해 백금과 같은 귀금속의 사용이 불가피하고 백금의 제한된 매장량과 높은 가격으로 인해 상용화가 늦어지고 있다. 그래서 많은 연구자들이 합금 촉매 또는 비귀금속 촉매를 이용한 전극 개발에 집중하고 있다. 알칼리 분위기에서 저가의 전이 금속들이 백금과 비슷한 활성을 보이고 고체 음이온 교환막이 개발됨에 따라 최근 알칼리 연료전지가 다시금 큰 주목을 받고 있다. 그러나 고분자 연료전지와는 달리 아직 촉매나 전해질막, 이오노머의 특성 및 메커니즘에 관해 별로 알려진 것이 없다. 본 연구에서는 직접 개발한 세공충진막 형태의 탄화수소계의 음이온 교환막과 비귀금속 공기극 촉매를 이용하여 막전극접합체(MEA)를 개발하였고 촉매 및 이오노머 함량과 같은 전극 조성, 막전극접합체의 제조 및 체결, 가습이나 가스조성 등의 단위전지 운전조건과 같은 다양한 변수에 대해에 최적 조건을 도출하고자 하였다. 공기극 촉매는 Cu-Fe/C를 이용한 상용 촉매를 이용하였고 이오노머의 경우는 탄화수소계의 상용 제품을 사용하였으며 음이온 교환막에 전극층을 형성하기 위해서는 스프레이 공정을 이용하였다. 단위전지를 통해 성능을 확인하였고 임피던스 및 CV를 통해 전기화학적인 특성을 규명하였다. 조건의 최적화를 통해 상당한 성능 향상을 이루었으나 추가적인 성능 향상 및 내구성 확보 등에 대해 계속적인 실험을 진행할 예정이다.

• Transactions of the Korean hydrogen and new energy society
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• v.18 no.4
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• pp.391-398
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• 2007

The covalently cross-linked sulfonated polyetheretherketone (CL-SPEEK) membrane was prepared by four-step synthesis of sulfonation-sulfochlorination, partial reduction, lithiation, and cross-linking, and its electrochemical and mechanical properties were investigated for water electrolysis application. The prepared ion exchange membranes showed good electrochemical and mechanical properties; proton conductivity of 0.116 S/cm at $80^{\circ}C$, water uptake of 44.6%, ion exchange capacity of 1.75 meq/g-dry-memb., tensile strength of 64.25 MPa and elongation of 61.11%. The membrane electrode assembly (MEA) with homemade membranes were prepared by non-equilibrium impregnation-reduction (I-R) method. Especially, the electrochemical surface area (ESA) and roughness factor of CL-SPEEK electrolyte by cyclic voltammetry method were 23.46 $m^2/g$ and 307.3 $cm^2-Pt/cm^2$, respectively. The prepared MEA was used in the unit cell of water electrolysis and the cell voltage was 1.81 V at 1 A/$cm^2$ and $80^{\circ}C$, with platinum loadings of 1.31 mg/$cm^2$.