• 한국수소및신에너지학회논문집
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• 제28권5호
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• pp.433-439
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• 2017

The high temperature performance of PEM type electrolyser at $120^{\circ}C$ based on covalently cross-linked sulfonated poly ether ether ketone (SPEEK) composie membrane was investigated. Ion conductivity and other properties of SPEEK membrane were improved by adding heteropoly acid and Ceria. The membrane electrode assemblies were prepared using commercial PtC and nano-sized $IrRuO_2$ catalyst by electro-spraying and decal process. Voltage efficiency of MEA equipped with SPEEK membrane was slightly better than that of $Nafion^{(R)}$ membrane, due to its higher proton conductivity at high temperature. The cell performance of MEA with CL-SPEEK/Cs-TSiA/Ceria is 1.71 V at $1A/cm^2$ and $120^{\circ}C$.

• 한국수소및신에너지학회논문집
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• 제27권5호
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• pp.478-484
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• 2016

Polyether ether ketone (PEEK) composite membranes have been intensively investigated for polymer electrolyte membrane water electrolysis (PEMWE). Covalently linked (CL) sulfonated polyether ether ketone (SPEEK) and cellulose polymer composite membranes were prepared and characterized. Polyether ether ketone (PEEK) and cellulose were sulfonated and then were covalently linked by 1,4-diiodobutane to produce covalently linked SPEEK and cellulose polymer composite membranes. The composite membranes showed better thermostability and electrochemical properties than SPEEK. The membranes were prepared by sol-gel casting method. CL-SPEEK/Cellulose composite membrane featured 0.2453 S/cm of proton conductivity at $80^{\circ}C$ which was better than that of Nafion.

• 방사선산업학회지
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• 제5권2호
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• pp.151-157
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• 2011

Crosslinked SPEEK/PVDF membrane were prepared by EB radiation method with various contents of PVDF. The prepared membranes were subjected to a comparative study of proton exchange membranes for fuel cell appreciations. The crosslinked SPEEK/PVDF membranes were characterized by using DMA, DSC and SAXS. The DMA data indicate that the ionic modulus values and cluster $T_g$ decrease with increasing PVDF content. Thus, it was suggested that the number of clustering in the crosslinked membranes can be reduced with increasing PVDF content. The DSC results were shown that the degree of crystalline of the membrane increased with increasing PVDF content. The morphology of the crosslinkied membranes was shown that with increasing PVDF content, the number of crystalline domain of the SPEEK/PVDF membranes increased but ionic aggregation of the membranes decreased. The water uptake behavior, ionic exchange capacity (IEC) and proton conductivity were decreased with increasing PVDF content. The overall findings suggest that the crosslinked membranes offer the possibility for improving the performance of PEMFC, provided that the membranes have thermal and hydration stability.

• 폴리머
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• 제36권2호
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• pp.155-162
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• 2012

전기방사 방법으로 sulfonated poly(ether ether ketone) (SPEEK) 나노섬유를 제조하고, 압축성형법으로 고분자 전해질막 연료전지(polymer electrolyte membrane fuel cell, PEMFC)용 나노섬유막을 제조하였다. SPEEK의 최대 설폰화율은 95% 이었고 초기 열분해 온도는 약 $280^{\circ}C$로 PEEK 보다 낮았으며 접촉각은 설폰화도가 증가함에 따라 감소하였다. 전기방사 나노섬유의 최적 인가전압, 유속, 방사거리(tip to collector distance, TCD) 및 농도는 각각 22 kV, 0.3 mL/hr, 5 cm, 23 wt% 이었고 평균 섬유직경은 47.6 nm 이었다. 한편, SPEEK 이온교환 나노섬유막의 함수율 및 이온교환용량은 설폰화 시간과 설폰화제 함량이 증가함에 따라 증가하였으며 최적값은 각각 20%, 2.03 meq/g으로 Nafion 117 보다 우수하였다. 막의 전기저항은 설폰화 시간이 증가함에 따라 감소하였고 그 값은 0.58~0.06 ${\Omega}{\cdot}cm^2$로 측정되었다. 또한 막의 수소이온전도도는 설폰화 시간이 증가함에 따라 증가하였으며 최대 0.099 S/cm로 Nafion 117 보다 우수하였다.

• 한국수소및신에너지학회논문집
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• 제16권1호
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• pp.40-48
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• 2005

Until recently, only perfluorinated ionomer membrane such as Nation and Aciflex practically could be successfully used in water splitting. However, these membrane are limited by high cost and loss of membrane performance such as proton conductivity at elevated temperature above 80$^{\circ}C$. The sulfonated aromatic polymers such as PEEK and PSf, polyimides, and polybenzimidazoles are expected to have lower production cost as well as satisfactory chemical and electrochemical properties. HPAs and sulfonated polymers could have a significant influence on water electrolysis performance at elevated temperatures above 80$^{\circ}C$, but these phenomena have received relatively little attention until now. Therefore, it would be desirable to investigate the interrelation between the HPA and sulfonated polymer, such as SPEEK. The SPEEK membrane were prepared by the sulfonation of PEEK, and HPA was blended with SPEEK to increase the mechanical strength and electrochemical characteristics. As a results, electrochemical characteristics such as proton conductivity and ion exchange capacity were improved with the addion of 0.5 g HPA. And the properties of polymer electrolyte, SPEEK/HPA were better than Nation membrane at elevated temperature above 80$^{\circ}C$.

• 전기화학회지
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• 제12권2호
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• pp.167-172
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• 2009

Direct methanol fuel cells(DMFCs) are receiving significant attention in the portable power source and electric vehicular transportation because of its high energy efficiency as liquid fuel, low cost, and no requirement of fuel reforming process. In this study, we synthesized the Sulfonated poly(ether ether ketone) (SPEEK) to evaluate the possibility of use as a proton exchange membrane for DMFC. And poly(vinylidienedifluoride) (PVDF) was used to increase proton conductivity in SPEEK and simultaneously to prevent methanol transport through the cross linked membrane. Furthermore, in order to improve the electrical composite properties for DMFC applications.

• 한국수소및신에너지학회논문집
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• 제26권6호
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• pp.524-531
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• 2015

To improve the electrochemical and mechanical characteristics, engineering plastic of the sulfonated polyether ether ketone (SPEEK) as polymer matrix was prepared in the sulfonation reaction of polyether ether ketone (PEEK). The SPEEK organic-inorganic blended composite membranes were prepared by sol-gel casting method. It was loaded with the highly dispersed ceria and cesium-substituted molybdosilicic acid (Cs-MoSiA) and 1,4-diiodobutane which was cross-linking agent contents of $10{\mu}L$. Cs-MoSiA was added to increase proton conductivity. Ceria ($CeO_2$) was used as a free radical scavenger which degrade the membrane in polymer electrolyte membrane water elctrolysis (PEMWE). In conclusion, CL-SPEEK/Cs-MoSiA/Ceria 1% composite membrane showed high proton conductivity 0.2104 S/cm at $25^{\circ}C$ which was better than Nafion 117 membrane.

• 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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• 제33권2호
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• pp.164-175
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• 2022

In this work, sulfonated poly (ether ether ketone) (SPEEK) composite membranes including strontium zirconate (SrZrO₃) were fabricated by the electrospinning method. Fourier-transform infrared spectroscopic analysis and X-ray diffraction analysis were used to identify the chemical structure and the crystallinity of SrZrO₃ and electrospun composite membranes. The thermal stability of the pure SPEEK and SPEEK/SrZrO₃ electrospun composite membranes were investigated by using thermogravimetric analysis. The physicochemical properties and proton conductivity were enhanced with the addition of different weight ratio of SrZrO₃ nanofiller (2, 4 and 6 wt%) in SPEEK polymer. The optimized SPEEK/SrZrO₃-4 electrospun membrane containing 4 wt% of SrZrO₃ showed a high proton conductivity compared to other electrospun SPEEK/SrZrO₃ composite membranes. The results indicate that electrospun composite membranes incorporating these perovskite nanofillers should be explored as potential candidates for use in proton exchange membrane fuel cells.

• 한국수소및신에너지학회논문집
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• 제22권1호
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• pp.1-12
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• 2011

To improve the mechanical properties, such as durabilities and antioxidative characteristics, the covalently cross-linked (CL-) SPEEK (sulfonated polyether ether ketone)/Cs-substituted HPA (heteropoly acid) organic-inorganic composite membranes (CL-SPEEK/Cs-HPAs), have been intensively investigated. The composite membrane were prepared by blending cesium-substituted HPAs (Cs-HPAs), including tungstophosphoric acid (TPA), molybdophosphoric acid (MoPA), and tungstosilicic acid (TSiA) with cross-linking agent content of 0.01 mL. And composite electrolytes composed of Cs-HPAs, prepared by immersion (imm.) and titration (titr.) methods to increase the stability of HPAs in water, were applied to polymer electrolyte membrane electrolysis (PEME). As a result, the proton conductivity of Cs-substituted composite membranes increased rapidly over $60^{\circ}C$ but mechanical properties, such as tensile strength, decreased in accordance with added Cs content. The bleeding-out of Cs-TPA membranes by titration method (50 vol.% Cs) decreased steadily to 2.15%. In the oxidative stability test by Fenton solution, the durability of membranes with Cs-HPA significantly increased. In case of CL-SPEEK/ Cs-TPA membrane, duration time increased more than 1200 hours. It is expected that even though CL-SPEEK/Cs-MoPA membrane shows the high proton conductivity, electrocatalytic activity and cell voltage of 1.80 V for water electrolysis, the CL-SPEEK/Cs-TPA (imm.) is more suitable as an alternative membrane in real system with the satisfactory proton conductivity, mechanical properties, anti-oxidative stability and cell voltage of 1.89 V.