Proton Mobility in Sulfonated PolyEtherEtherKetone (SPEEK): Influence of Thermal Crosslinking and Annealing

Knauth, Philippe; Pasquini, Luca; Maranesi, Brunella; Pelzer, Katrin; Polini, Riccardo; Vona, Maria Luisa Di

doi:10.1002/fuce.201200120

Cited by 27 publications

(20 citation statements)

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“…The peruorinated sulfonated polymer Naon™ was discovered in the 1960's; 5 sulfonated aromatic polymers are alternative, less expensive ionomers. [9][10][11] Anion-conducting membranes have also many high technology applications, including water desalination, alkaline fuel cells or electrolysers (when the anion is hydroxide), or redox ow batteries. 8 We have analyzed the proton conductivity of these ionomers, based on the concepts of proton mobility, tortuosity and percolation of proton-conducting channels.…”

Section: Introductionmentioning

confidence: 99%

Anion-conducting sulfaminated aromatic polymers by acid functionalization

et al. 2015

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A simple synthesis technique for the preparation of anionic conducting membranes is presented. In the first step, poly-ether-ether-ketone (PEEK) reacts with chlorosulfonic acid to produce chlorosulfonated PEEK, which in a second step is transformed by reaction with a secondary amine, dimethyl- or diethylamine, into sulfaminated PEEK. The sulfaminated PEEK is cast and the membranes are functionalized in a last step by reaction with various aqueous acid solutions, including HCl, HBr, HNO3, H2SO4, and H3PO4. The spectroscopic, thermal, mechanical, permeability and electrical properties of the membranes are determined and discussed. The combination of appealing properties, such as high elastic modulus (∼1300 MPa), high thermal stability, low cation permeability, respectable anionic conductivity (2-4 mS cm-1), and a relatively simple and inexpensive synthesis make these new ionomers very promising for applications especially in acidic media, like in vanadium redox flow batteries

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Section: Introductionmentioning

confidence: 99%

Anion-conducting sulfaminated aromatic polymers by acid functionalization

et al. 2015

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“…The linear part of the semi-logarithmic mobility plot in Figure 4 can be extrapolated to c = 0 (infinite dilution). The extrapolated value at 25°C is somewhat lower than the proton mobility in pure water (≈3.6 × 10 −3 cm 2 /V.s (Kortüm, 1965)). This is due to the fact that the hydrated domains have only a reduced size (expressed by the "porosity") and are not straight, but tortuous, so that protons have to move a longer way to cross the membrane as compared to the membrane thickness.…”

Section: Proton Conductivitymentioning

confidence: 69%

“…In absence of a complete analysis, the interface term, although reputedly related to the Schröder paradox (Freger, 2009), is thus difficult to assess. The electrostatic term, which can be written analytically only with the simplified linearized Poisson-Boltzmann equation (Kortüm, 1965;Hamann et al, 2007), can be described in general only numerically, as done for instance in the early work by Gregor and coworkers (Lazare et al, 1956). These two terms are thus difficult to express in an analytical form and hard to predict.…”

Section: Hydration Propertiesmentioning

confidence: 99%

“…Whereas polymer electrolytes for lithium batteries must work in absence of water to avoid corrosion and decomposition reactions, polymer electrolytes used in fuel cells and redox flow batteries contain significant amounts of water in hydrated nanometric domains that assure the proton or anion conduction inside a matrix made by the polymer backbones (Springer et al, 1991;Zawodzinski et al, 1993;Kreuer, 2001;Kreuer et al, 2004;Smitha et al, 2005;Diat and Gebel, 2008;Peckham et al, 2008;Hickner, 2012;Wu et al, 2013). Such polymers with a micro-phase separation between hydrated ionic conducting domains and electronically insulating polymer domains are also called ionomers.…”

Section: Introductionmentioning

confidence: 99%

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Hydration and Proton Conductivity of Ionomers: The Model Case of Sulfonated Aromatic Polymers

Knauth¹,

Vona²

2014

Front. Energy Res.

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The hydration of proton-conducting ionomers is described in terms of a simplified model, where only osmotic and elastic contributions to the Gibbs free energy of hydration are considered. Although only two physically meaningful parameters are used-the deformation parameter, inversely proportional to the elastic modulus of the ionomer, and the free volume parameter-simulated hydration isotherms are in good agreement with the experiment. The proton mobility u inside the electrolyte solution of the ionomer is calculated from the proton conductivity determined at various hydration numbers. Its variation with the proton concentration c reveals the percolation threshold of hydrated nanometric channels and the tortuosity of the membrane. Above the percolation threshold, a power law u~c −3 is observed, in agreement with the "universal" law for 3-dimensional percolation. The proton conductivity σ shows at 100°C a maximum of 0.2 S/cm at a hydration number 90. The σ = f(c) plot allows to predict, which hydration conditions are necessary for a desired area specific resistance.

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“…The ratio of the fluoridei on diffusion coefficient in aqueous NaF solution D8 and in the ionomers D can be used to estimate the tortuosity and porosity of the membranes, according to Equation (5), as caling equation: [35,36] D…”

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confidence: 99%

Fluoride‐ion‐conducting Polymers: Ionic Conductivity and Fluoride Ion Diffusion Coefficient in Quaternized Polysulfones

et al. 2015

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We describe the three-step synthesis of a new polymeric fluoride ion conductor based on the fully aromatic polymer polysulfone (PSU). In the first step, PSU is chloromethylated (CM-PSU) using reagents (i.e., stannic chloride, paraformaldehyde, and trimethylchlorosilane) that are less toxic than those used in the standard procedure. In the second step, CM-PSU reacts with a tertiary amine (trimethylamine or 1,4-diazabicyclo[2.2.2]octane) to form quaternary ammonium groups fixed on the PSU backbone and mobile chloride counter-anions. The chloride ions can, in a third step, be exchanged with fluoride ions by immersion of the ionomer in NaF solution. The fluoride ion conductivity reaches 3-5 mS cm(-1) at 25 °C and 5-10 mS cm(-1) at 40 °C. We determined the F(-) diffusion coefficient in these ionomers by pulsed gradient spin-echo (PGSE) high-resolution magic angle spinning (HRMAS) nuclear magnetic resonance (NMR) spectroscopy and by impedance spectroscopy using the Nernst-Einstein relation. The diffusion coefficients determined by the two methods are in good agreement, ranging from 2 to 4×10(-10) m(2) s(-1) . The porosity and tortuosity of the ionomer membranes can be estimated.

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Proton Mobility in Sulfonated PolyEtherEtherKetone (SPEEK): Influence of Thermal Crosslinking and Annealing

Cited by 27 publications

References 48 publications

Anion-conducting sulfaminated aromatic polymers by acid functionalization

Anion-conducting sulfaminated aromatic polymers by acid functionalization

Hydration and Proton Conductivity of Ionomers: The Model Case of Sulfonated Aromatic Polymers

Fluoride‐ion‐conducting Polymers: Ionic Conductivity and Fluoride Ion Diffusion Coefficient in Quaternized Polysulfones

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