• 한국신재생에너지학회:학술대회논문집
• /
• 2010.11a
• /
• pp.85.2-85.2
• /
• 2010

There is widespread effort to develop polymer membranes in place of Nafion for high temperature polymer electrolyte membrane fuel cell(PEMFC). In our study, SiO2 membranes are arranged by electrospinning method. For impregnation solution, the modified sulfonated poly(ether ether ketone)(SPEEK) polymer is prepared from sulfonation, sulfochlorination, partial reduction and lithiation reaction. The modified polymer is cross-linked with 1,4-diiodobetane in NMP solvent and then blended with Heteropoly acid(HPA). The characterization of membranes is confimed by FT-IR, Thermogravimetry(TGA), water uptake test and single cell performance test for PEMFC, etc. The composite membrane shows satisfactory thermal and mechanical properties. Beside, The membrane exhibits good ion exchange capacity and high proton conductivity. As a result, The composite membrane is promising as an alternative membrane in high temperature PEMFC.

• Journal of Hydrogen and New Energy
• /
• v.16 no.1
• /
• pp.40-48
• /
• 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$^{\circ}C$.

• Journal of Hydrogen and New Energy
• /
• v.20 no.2
• /
• pp.95-103
• /
• 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
• /
• v.22 no.1
• /
• pp.1-12
• /
• 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.

• Journal of Hydrogen and New Energy
• /
• v.20 no.3
• /
• pp.194-201
• /
• 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.

• Journal of Hydrogen and New Energy
• /
• v.21 no.1
• /
• pp.26-34
• /
• 2010

The electrocatalystic prperties of Pt-Co and Pt-Ni with heteropolyacids (HPAs) entrapped in covalently cross-linked sulfonated poly(ether ether ketone) (CL-SPEEK)/HPA membranes were investigated for water electrolysis. The HP As, including molybdophosphoric acid (MoPA), and tungstophosphoric acid (TPA) were both used as membrane additives and electrocatalysts. The membrane electrode assembly (MEA) was prepared by a nonequilibrium impregnation-reduction (I-R) method. $Pt(NH_3)_4Cl_2$, $NiCl_2$ and $CoCl_2$ as electrocatalytic materials and $NaBH_4$ as reducing agent were used. I order to enhance electrocatalytic activity, the catalyst layer prepared above was electrodeposited (Dep) with HP A. Surface morphologies and physico-chemical properties of MEA were investigated by means of SEM, EDX and XRD. The electrocatalytic properties of composite membranes such as the cell voltage and coulombic charge in CV were in the order of magnitude: CL-SPEEK/MoPA40 (wt%) > CL-SPEEK/TPA30 > Nafion117. In the optimum cell applications for water electrolysis, the cell voltage of Pt/CL-SPEEK-MoPA40/Pt-Co (Dep-MoPA) and Pt/CL-SPEEK-TPA30/Pt-Co (Dep-TPA) was 1.75 Vat $80^{\circ}C$ and $1\;A/cm^2$ and voltage efficiency was 87.1%. Also, the observed activity of Pt-Co (84:16 atomic ratio by EDX) is a little higher than that of Pt-Ni (86: 14). The current density peak of electrodeposited electrodes were better a little than those of unactivated electrodes based on the same membranes.

• Journal of Hydrogen and New Energy
• /
• v.17 no.2
• /
• pp.149-157
• /
• 2006

Hydrogen as new energy sources is highly efficient and have very low environmental emissions. The proton exchange membrane fuel cell (PEMFC) is an emerging technology that can meet these demands. Therefore, the preparation of stable polymeric membranes with good proton conductivity and durability are very important for hydrogen production via water electrolysis with PEM at medium temperature above $80^{\circ}C$. Currently Nafion of Dupont and Aciflex of Asahi, etc., solid polymer electrolytes of perfluorosulfonic acid membrane, are the best performing commercially available polymer electrolytes. However, these membrane have several flaws including its high cost, and its limited operational temperature above $80^{\circ}C$. Because of this, significant research efforts have been devoted to the development of newer and cheaper membranes. In order to make up for the weak points and to improve the mechanical characteristics with cross -linking, acid-base complexes were prepared by the combination PSf-co-PPSS-$NH_2$ with PEEK-$SO_3H$. The results showed that the proton conductivity decreased in 17.6% and 40% but tensile strength increased in 78% and 98%, about $20.65\;{\times}\;10^6N/m^2$, in comparison with SBPSf/HPA and SPEEK/HPA complex membrane.