• Journal of Hydrogen and New Energy
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• v.22 no.1
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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.

• Membrane Journal
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• v.20 no.4
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• pp.278-289
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• 2010

A series of composite membranes based on sulfonated poly(arylene ether sulfone) (SPAES) were prepared via addition of tetraethyl orthosilicate (TEOS) and solution casting method. The morphological structure, water uptake, proton conductivity of the resulting composite membranes were extensively investigated as function of the content of TEOS. By the sol-gel reaction, TEOS molecules were not completely converted to $SiO_2$ particles, but formed only oligomer-type. Also, EDS confirms that the resulting silicon dioxide was homogeneously distributed in the composite membranes. As the content of TEOS increased, the prepared membranes increased water uptake and proton conductivity at high temperature and low relative humidity condition. In particular, considerably high proton conductivity (0.015 S/cm) at $120^{\circ}C$ and 48%RH was demonstrated in the composite membrane containing 200% TEOS, which is 10 times greater than that of unmodified SPAES membrane. Also, the composite membranes were found to have enhanced thermal stability compared to the unmodified membrane.

• 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.

• Polymer(Korea)
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• v.36 no.2
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• pp.155-162
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• 2012

Sulfonated poly(ether ether ketone) (SPEEK) nanofibers were prepared by electrospinning. The nanofibrous membrane for polymer electrolyte membrane fuel cell (PEMFC) was fabricated by compression molding. The maximum degree of sulfonation was 95% and the initial thermal degradation temperature was $280^{\circ}C$ and it's value was lower than that of PEEK. The contact angle of SPEEK increased with decreasing the degree of sulfonation. The optimum voltage, flow rate, tip to collector distance (TCD) and concentration of electrospinning conditions were 22 kV, 0.3 mL/hr, 15 cm, and 23 wt%, respectively. The average nanofibrous diameter was 47.6 nm. The water uptake and ion exchange capacity of SPEEK nanofibrous membrane increased with increasing the sulfonation time and the amount of sulfonating agent. The electrical resistance and proton ionic conductivity of SPEEK membrane increased with decreasing and increasing the sulfonation time, respectively. Their values were 0.58~0.06 ${\Omega}{\cdot}cm^2$and 0.099 S/cm.

• Membrane Journal
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• v.21 no.1
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• pp.1-12
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• 2011

Partially fluorinated poly(arylene ether sulfone) block ionomer membranes with different branch degree for fuel cell applications were investigated. A sulfonable monomer, a non-sulfonable monomer and a trifunctional branching agent were synthesized and the sulfonable monomer was oligomerized to obtain block structures. The oligomer was then further polymerized with the non-sulfonable monomer and the branching agent. The mole ratio of oligomer : non-sulfonable monomer was fixed at 4:6 and the content of the branching agent was varied from 0 to 2 mol% (BBC-40Bx). Post-sulfonation of BBC-40Bx was carried out using chlorosulfonic acid (CSA) (SBBC-40Bx). All the synthesized compounds were characterized by $^1H$-NMR, $^{19}F$-NMR and FT-IR. It was confirmed that the ion exchange capacity (IEC), water uptake and ion conductivity of SBBC-40Bx increased with the increment of branching agent content.

• Korean Chemical Engineering Research
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• v.61 no.2
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• pp.189-195
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• 2023

As a PEMFC (Polymer Exchange Membrane Fuel Cell) cathode catalyst, Pt-Co/C has recently been widely used because of its improved durability. In a fuel cell, electrodes and electrolytes have a close influence on each other in terms of performance and durability. The effect on the electrochemical durability of the electrolyte membrane when Pt-Co/C was replaced in the Pt/C electrode catalyst was studied. The durability of Pt-Co/C MEA (Membrane Electrode Assembly) was higher than that of Pt/C MEA in the electrochemical accelerated degradation process of PEMFC membrane. As a result of analyzing the FER (Fluorine Emission Rate) and hydrogen permeability, it was shown that the degradation rate of the membrane of Pt-Co/C MEA was lower than that of Pt/C MEA. In the OCV (Open Circuit Voltage) holding process, the rate of decrease of the active area of the Pt-Co/C electrode was lower than that of the Pt/C electrode, and the amount of Pt deposited on the membrane was smaller in Pt-Co/C MEA than in Pt/C MEA. Pt inside the polymer membrane deteriorates the membrane by generating radicals, so the degradation rate of the membrane of Pt/C MEA with a high Pt deposition rate was higher than Pt-Co/C MEA. When the Pt-Co/C catalyst was used, the electrode durability was improved, and the amount of Pt deposited on the membrane was also reduced, thereby improving the electrochemical durability of the membrane.