• Transactions of the Korean hydrogen and new energy society
• /
• 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.

• Transactions of the Korean hydrogen and new energy society
• /
• v.28 no.5
• /
• pp.433-439
• /
• 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 $120^{\circ}C$.

• Transactions of the Korean hydrogen and new energy society
• /
• v.29 no.5
• /
• pp.411-418
• /
• 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.

• Korean Chemical Engineering Research
• /
• v.45 no.4
• /
• pp.391-395
• /
• 2007

A new electrode binder mixed with sulfonated poly (ether ether ketone) (sPEEK) and Nafion is prepared and investigated as an anode binder for direct methanol fuel cell (DMFC). The mixed binder (95 wt% sPEEK/5 wt% Nafion) shows high proton conductivity and methanol transport rate as well as no dissolution and brittleness. The effect of content as an anode binder on the performance of the cell with the given cathode is investigated. The unit cell with the anode containing 10wt% mixed binder showed the highest cell performance.

• Transactions of the Korean hydrogen and new energy society
• /
• 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.

• Transactions of the Korean hydrogen and new energy society
• /
• 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.

• Transactions of the Korean hydrogen and new energy society
• /
• v.26 no.6
• /
• pp.524-531
• /
• 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.

• Transactions of the Korean hydrogen and new energy society
• /
• v.25 no.6
• /
• pp.561-569
• /
• 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.

• Transactions of the Korean hydrogen and new energy society
• /
• v.18 no.4
• /
• pp.391-398
• /
• 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/$cm^2$.

• Transactions of the Korean hydrogen and new energy society
• /
• v.26 no.3
• /
• pp.212-220
• /
• 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.