• 한국수소및신에너지학회논문집
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• 제29권5호
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• pp.411-418
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• 2018

The polymer electrolyte membranes, CL-SPEEK/Cellulose composite membrane I, II, III with the improved electrochemical and mechanical properties were prepared and characterized. The engineering plastic polyether ether ketone (PEEK) and cellulose were sulfonated and cross-linked. The membranes were prepared by sol-gel casting method with different amount of cross-linking reagent. In conclusion, the composite membranes I, II, III showed improved thermostability, tensile strength and oxidative durability. Proton conductivity of the membranes was also improved and the composite membrane I showed 0.1312 S/cm at $80^{\circ}C$ which was the best of those composite membranes.

• 멤브레인
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• 제18권4호
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• pp.274-281
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• 2008

술폰화 폴리아릴렌에테르술폰 공중합체를 직접 중합법으로 합성하고 공유 가교하여 연료전지용 고분자 전해질 막을 제조하였다. 최적의 전해질 막 제조를 위하여 가교제의농도를 $30{\sim}90\;v/v%$ 및 가교시간을 30분 내지 720분의 범위에서 다양한 조성의 전해질 막 제조실험이 수행되었으며 FT-IR분광법 및 열 중량분석, 수소 이온 전도도 측정 등을 통해 전해질 막의 기본 특성들을 평가하였다. 수소 이온 전도도는 가교도에 따라 감소하는 것으로 나타났으며, 물 흡수율 및 메탄올 투과도도 함께 낮아짐을 알 수 있었다.

• 한국수소및신에너지학회논문집
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• 제20권3호
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• pp.194-201
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• 2009

The e1ectrocatalytic properties of heteropolyacids(HPAs) entrapped in covalently cross-linked sulfonated polyetheretherketone(CL-SPEEK/HPA) membranes have been studied for water electrolysis. The HPAs, including tungstophosphoric acid(TPA), molybdophosphoric acid(MoPA), and tungstosilicic acid(TSiA) were used as additives in the composite membranes. The MEA was prepared by a non-equilibrium impregnation-reduction(I-R) method, using reducing agent, sodium borohydride(NaBH4) and tetraamineplatinum(II) chloride(pt(NH$_3$)$_4$Cl$_2$). The electrocatalytic properties of composite membranes such as the cell voltage were in the order of magnitude CL-SPEEKlMoPA40 (wt%) > /TPA30 > /TSiA40. In the optimum cell applications for water electrolysis, the cell voltage of PtlPEM/Pt-Ru MEA with CL-SPEEKlTPA30 membrane was 1.75 V at 80$^{\circ}$C and I A/cm$^2$ and this voltage carried lower than that of 1.81 V of Nafion 117. Consequently, in regards of electrochemical and mechanical characteristics and oxidation durability, the newly developed CL-SPEEKITPA30 composite membrane exhibited a better performance than the others, but CLSPEEKlMoPA40 showed the best electrocatalytic activity (1.71 Vat 80$^{\circ}$C and 1 A/cm$^2$) among the composite membranes.

• 한국수소및신에너지학회논문집
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• 제18권4호
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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/$cm^2$.

• 한국수소및신에너지학회논문집
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• 제25권6호
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• pp.561-569
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• 2014

Ceria ($CeO_2$) was used to increase the durability of the membrane in the polymer electrolyte membrane water electrolysis (PEMWE) circumstance. The sulfonated polyether ether ketone (SPEEK) as polymer matrix was prepared in the sulfonation reaction of polyether ether ketone (PEEK) to improve electrochemical characteristics. After sulfonation reaction, the organic-inorganic blended composite membranes were prepared by means of sol-gel casting method with loading the highly dispersed $CeO_2$ and Cs-substituted molybdophosphoric acid (Cs-MoPA) with cross-linking agent (tetrapropyl orthosilicate). Consequently, the composite membrane CL-SPEEK/Silane 4wt%/Cs-MoPA/Ceria(1%) showed the improved characteristics such as 82% of water content, 0.11136 S/cm of proton conductivity at $80^{\circ}C$, 55.50 MPa of tensile strength and 4.37% of breeding out of MoPA.

• 한국수소및신에너지학회논문집
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• 제26권3호
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• pp.212-220
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• 2015

The engineering plastic of sulfonated polyether ether ketone (SPEEK) as a polymer matrix has been developed in this lab to replace Nafion, solid polymer electrolytes of perfluorosulfonic acid membrane which has several flaws such as high cost, and limited operational temperature above $80^{\circ}C$. The SPEEK was prepared in the sulfonation reaction of polyether ether ketone (PEEK). The organic-inorganic blended composite membranes were prepared by sol-gel casting method with loading the highly dispersed ceria and cesium-substituted tungstosilicic acid (Cs-TSiA) with cross-linking agent contents of 0.01 mL. In conclusion, CL-SPEEK/Cs-TSiA/ceria 1% membrane showed the optimum results such as 0.1882 S/cm of proton conductivity at $80^{\circ}C$, and 99.61 MPa of tensile strength which were better than Nafion 117 membrane.

• 한국수소및신에너지학회논문집
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• 제20권2호
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• pp.95-103
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• 2009

In order to improve the electrochemical, mechanical and electrocatalytic characteristics, engineering plastic of polyether ether ketone (PEEK) as polymer matrix was sulfonated (SPEEK) and the organic-inorganic blend composite membranes has been prepared by loading heteropoly acids (HPAs), including tungstophosphoric acid (TPA), molybdophosphoric acid (MoPA), and tungstosilicic acid (TSiA). And then these were covalently cross-linked (CL-SPEEK/HPA) as the electrolyte and MEA of polymer electrolyte membrane electrolysis (PEME). As a result, the optimum reaction conditions of CL-SPEEK/HPA was established and the electrochemical characteristics such as ion conductivity ($\sigma$) were in the order of magnitude: CL-SPEEK /TPA30 (${\sigma}=0.128\;S/cm^{-1}$) < /MoPA40 (${\sigma}=0.14\;S/cm^{-1})$ < /TSiA30 (${\sigma}=0.22\;S/cm^{-1}$) at $80^{\circ}C$, and mechanical characteristics such as tensile strength: CL-SPEEK /TSiA30 $\fallingdotseq$ /MoPA40 < /TPA30. Consequently, in regards of above characterisitics and oxidation durability, the CL-SPEEK/TPA30 exhibited a better performance in PEME than the others, but CL-SPEEK/MoPA40 showed the best electrocatalytic activity of cell voltage 1.71 V among the composite membranes. The dual effect of higher proton conductivity and electrocatalytic activity with the addition of HPAs, causes a synergy effect.

• 한국수소및신에너지학회논문집
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• 제25권2호
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• pp.151-160
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• 2014

CL-SPEEK/Cs-TPA/$CeO_2$ composite membrane was prepared for polymer electrolyte membrane water electrolysis (PEMWE). In order to improve the electrochemical, mechanical, durabilities and electrocatalytic characteristics, engineering plastic of polyether ether ketone (PEEK) as polymer matrix was sulfonated and the organic-inorganic blend composite membranes was prepared by loading cesium-substituted tungstophosphoric acid (Cs-TPA) by titration method with cross-linking agent contents of 0.01mL. Ceria ($CeO_2$) was used to scavenge free radicals which attack the membrane in the PEMWE circumstance and to increase the duration of the membrane. CL-SPEEK/$Cs_{(1)}$-TPA/CeriaIn conclusion, 1% membrane showed the optimum results such as 0.119 S/cm at $80^{\circ}C$ of proton conductivity and 62MPa of tensile strength.

• 한국수소및신에너지학회논문집
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• 제23권5호
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• pp.437-447
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• 2012

Ceria ($CeO_2$) was used to scavenge free radicals which attack the membrane in the polymer electrolyte membrane water electrolysis (PEMWE) circumstance and to increase the duration of the membrane. In order to improve the electrochemical, mechanical and electrocatalytic characteristics, engineering plastic of the sulfonated polyether ether ketone (SPEEK) as polymer matrix was prepared in the sulfonation reaction of polyether ether ketone (PEEK) and the organic-inorganic blended composite membranes were prepared by sol-gel casting method with loading the highly dispersed ceria and cesium-substituted tungstophosphoric acid (Cs-TPA) with cross-linking agent contents of 0.01 mL. In conclusion, CL-SPEEK/Cs-TPA/ceria (1%) membrane showed the optimum results such as 0.130 S/cm of proton conductivity at $80^{\circ}C$, 2.324 meq./g-dry-membrane of ion exchange capacity and mechanical characteristics, and 65.03 MPa of tensile strength which were better than Nafion 117 membrane.

• Applied Biological Chemistry
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• 제49권1호
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• pp.49-54
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• 2006

쌀 전분에 phosphorus oxychloride$(POCl_3)$를 단계별(전분 고형분 대비 $0.005{\sim}0.06%$)로 2시간 반응시켜 가교화 쌀 전분을 제조하고, 변성된 쌀 전분의 용해도, 팽윤력, RVA, DSC, X-ray 특성을 연구하였다. 팽윤력은 일반 쌀 전분 보다 다소 낮은 온도에서 증가되기 시작하였으나 그 이후는 모두 낮은 수치를 보여 가교화 쌀 전분이 일반 쌀 전분보다 완만한 상승을 나타내었다. 용해도는 가교화 쌀 전분이 일반 쌀 전분보다 전체적으로 낮은 결과를 나타내었고 $POCl_3$ 함량에 따른 유의적인 차이는 보이지 않았다. RVA 분석결과 가교화 쌀 전분이 일반 쌀전분보다 pasting temperature와 최고점도는 낮아졌고 holding strength와 final viscosity는 높은 경향을 나타내어 breakdown과 setback 은 낮은 것으로 나타났다. DSC 분석 결과 가교화 쌀 전분이 일반 쌀 전분보다 $T_o$, $T_p$, $T_c$가 감소하였으나 ${\Delta}H$의 경우 큰 차이가 나타나지 않았다. X-ray 회절분석 결과 일반 쌀 전분 보다 $POCl_3$ 함량에 따라 상대적 결정화도가 소폭 감소되는 결과를 나타내었으나 95% 신뢰도 수준에서 유의적인 차이는 없는 것으로 나타났다. 따라서 가교화 쌀 전분의 경우 전분입자가 $POCl_3$ 의해 강한 공유 결합을 형성함으로써 내열성, 내전단성의 성질이 생겨 호화가 일어난 후에 점도가 많이 낮아지지 않은 것으로 판단되며 전분의 결정형태에는 크게 영향을 미치지 않으나 전분의 무정형 부분에 영향을 주어 쌀 전분의 팽윤력, 용해도 및 pasting property등의 물리화학적 성질에 변화를 주는 것으로 판단되었다.