• Journal of Hydrogen and New Energy
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• v.20 no.2
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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.

• Journal of Hydrogen and New Energy
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• v.25 no.6
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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.

• Journal of Hydrogen and New Energy
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• v.25 no.2
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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.

• Journal of Hydrogen and New Energy
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• v.26 no.6
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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.

• Journal of Hydrogen and New Energy
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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/$cm^2$.

• Journal of Hydrogen and New Energy
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• v.29 no.5
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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.

• Proceedings of the Korean Powder Metallurgy Institute Conference
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• 2006.09a
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• pp.487-488
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• 2006

Novel bisphenol-based wholly aromatic poly(ether sulfone-ketone) copolymer containing pendant sulfonate groups were prepared by direct aromatic nucleophilic substitution polycondensation of 4,4-difluorobenzophenone, 2,2'-disodiumsulfonyl-4,4'-fluorophenylsulfone (40mole% of bisphenol A) and bisphenol A. Polymerization proceeded quantitatively to high molecular weight in N-methyl-2-pyrrolidinone at $180^{\circ}C$. Organic-inorganic composite membranes were obtained by mixing organic polymers with hydrophilic $SiO_2$ (ca. 20nm) obtained by sol-gel process. The polymer and a series of composite membranes were studied by FT-IR, $^1HNMR$, differential scanning calorimetry (DSC) and thermal stability. The proton conductivity as a function of temperature decreased as $SiO_2$ content increased, but methanol permeability decreased. The nano composite membranes were found to posse all requisite properties; Ion exchange capacity (1.2meq./g), glass transition temperatures $(164-183\;^{\circ}C)$, and low affinity towards methanol $(4.63-1.08{\times}10^{-7}\;cm^2/S)$.

• 한국신재생에너지학회:학술대회논문집
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• 2009.06a
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• pp.378-378
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• 2009

The ionic liquid-based sulfonated hydrocarbon composite membranes was prepared for use in anhydrous high temperature-polymer electrolyte fuel cells (HT-PEFCs). Ionic liquid behaves like water in the composite membranes under anhydrous condition. However the composite membranes show a low conductivity and high gas permeability as the content of ionic liquid increases due to its high viscosity and content of ionic liquid, respectively. Hence, in order to enhance the proton conductivity and to reduce the gas permeability of the composite membranes with low content of ionic liquids, the acid containing a common ion of ionic liquid was added to the composite membranes. The characterization of composite membranes was carried out using small-angle X-ray scattering (SAXS), thermogravimetric analyzer (TGA) and impedance spectroscopy. As a result, the composite membranes containing acid showed higher proton conductivity than those with no acid under the un-humidified condition due to a decrease in viscosity. In addition, the proton conductivity of composite membranes increased with increasing mole concentration of acid.

• Journal of Hydrogen and New Energy
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• v.21 no.4
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• pp.307-312
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• 2010

Poly (ether sulfone)s with Bisphenol-TP and Bisphenol-AF were prepared with Bisphenol-TP <4,4-dihydroxy tetraphenyl methane>, 4-Fluorophenyl sulfone, and Bisphenol-AF <4,4-(hexafluoroisopropylidene) diphenol> using Potassium carbonate in Sulfolane at $210^{\circ}C$. Sulfonated PBTP-AF were obtained by reaction of Chlorosulfuric acid with copolymers. A series of copolymers were studied by $^1H$-NMR spectroscopy, Differential Scanning Calorimeter (DSC), and Thermo Gravimetric Analysis (TGA). Sorption experiments were conducted to observe the interaction of polymers with water and methanol.

• Journal of the Korean Electrochemical Society
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• v.17 no.1
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• pp.44-48
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• 2014

Sulfonated poly(arylene ether sulfone)-cerium composite membranes with improved oxidative stability were prepared for proton exchange membrane fuel cell application. Oxidative stability of the composite membranes changed depending on the amount of incorporated metal. Their water uptake, IEC and proton conductivity were also affected. ICP analysis confirmed trace of cerium ion in the composite membranes and $^1H$-NMR indicated successful coordination of sulfonic acid groups with the metal ions. Increasing amount of the cerium ion resulted in decrease in proton conductivities and water uptake, but enhanced oxidative stabilities. A hydrogen peroxide exposure equipment was used for the test of oxidative stability of the composite membranes, which enabled to mimic fuel cell operating condition compared with conventional Fenton's test.