Sulfonated poly(arylene thioether phosphine oxide)s and poly(arylene ether phosphine oxide)s PBI-blend membranes and their performance in SO2 electrolysis

Cichon, Patrizia J.; Krüger, Andries J.; Krieg, H.M.; Bessarabov, Dmitri; Aniol, Karin; Kerres, Jochen

doi:10.1016/j.ijhydene.2015.11.147

Cited by 13 publications

(6 citation statements)

References 26 publications

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“…PBI membranes have exceptional performance characteristics in various electrochemical devices due to their high ionic conductivity when imbibed with various acid electrolytes. [16][17][18][19][20][21] To date, a large variety of PBI polymers have been synthesized and studied, and a sulfonated polybenzimidazole was selected for use in SDE applications due to its stability in the sulfuric acid environments present in the electrolyzer, 13 which has resulted in an increased focus on PBI for SDE applications over the past several years. 19,[22][23][24] These works focused on including different blends of PBI with high H 2 SO 4 imbibed concentrations (80 wt%) 19,24 during membrane preparation, partially fluorinated PBI, 22,24 and crosslinked PBI.…”

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confidence: 99%

Characterizing Voltage Losses in an SO₂Depolarized Electrolyzer Using Sulfonated Polybenzimidazole Membranes

Garrick

Wilkins

Pingitore

et al. 2017

J. Electrochem. Soc.

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The hybrid sulfur cycle has been investigated as a means to produce CO 2 -free hydrogen efficiently on a large scale through the decomposition of H 2 SO 4 to SO 2 , O 2 , and H 2 O, and then electrochemically oxidizing SO 2 back to H 2 SO 4 with the cogeneration of H 2 . The net effect is the production of hydrogen and oxygen from water. Recently, sulfonated polybenzimidazoles (s-PBI) have been investigated as a replacement for Nafion due to the ability to offer increased process efficiency through the generation of higher acid concentrations at lower potentials. Here, we measure the acid concentrations and individual potential contributions toward the overall operating voltage seen in the SO 2 -depolarized-electrolyzer. We then determine model parameters necessary to predict voltage losses in a cell over a wide range of operating temperatures, pressures, currents and reactant flow rates. The hydrogen production program at the U. S. Department of Energy is examining an array of distributed and centralized hydrogen facilities that could contribute to the hydrogen generation infrastructure.1 Thermochemical cycles are being considered for large scale, centralized facilities due to their potential for high efficiencies at low costs. These cycles involve a series of chemical reactions that result in the splitting of water at much lower temperatures (∼500-1000• C) than direct thermal dissociation (>2500 • C) and at much higher efficiencies than direct water electrolysis.2 Chemical species in these reactions are recycled resulting in the consumption of only energy and water to produce hydrogen and oxygen. Although there are hundreds of possible thermochemical cycles, the hybrid-sulfur (HyS) process is the only all-fluid, two step thermochemical cycle. 3-6The high temperature step (850-950• C) involves the decomposition of H 2 SO 4 to produce oxygen and sulfur dioxide via the following reaction:The SO 2 is separated, cooled, and sent to the SO 2 -depolarized electrolyzer (SDE). The resulting reactions at the anode and cathode, respectively, are:Thus, the overall reaction in the electrolyzer is represented as:Considerable progress was made in the last decade in lowering the operating voltage and increasing the current density of the SDE by moving from a microporous rubber diaphragm separator used by Westinghouse 7 to a perfluorinated sulfonic acid membrane (e.g., DuPont's Nafion). [8][9][10][11][12] For example, Westinghouse was only able to get the cell voltage down to 1.0 V at 400 mA/cm 2 , where we achieved 500 mA/cm 2 at 0.71 V and 1.2 A/cm 2 at 1.0 V using Nafion 212 (N212). However, to achieve overall process efficiency, concentrated sulfuric acid as well as low cell voltage at high current densities are * Electrochemical Society Member.* * Electrochemical Society Student Member. * * * Electrochemical Society Fellow.z E-mail: taylor.garrick@gm.com; weidner@cec.sc.edu necessary. The key issue when using membranes like Nafion that rely on water for their proton conductivity is that high acid concentrations dehydrate ...

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Characterizing Voltage Losses in an SO₂Depolarized Electrolyzer Using Sulfonated Polybenzimidazole Membranes

Garrick

Wilkins

Pingitore

et al. 2017

J. Electrochem. Soc.

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“…Even though the polymers are the best electrolyte membranes, those have been limited by the degradation of proton conductivity and mechanical strength above 80 °C and high cost . Accordingly, non‐fluorine polymers like sulfonated polyether ether ketone (SPEEK) are of significant interest due to their low costs and outstanding electrochemical properties . Our focus has been to complete the preparation of a series of heteropoly acids (HPAs) and CeO 2 included SPEEK system composite membranes for water electrolysis.…”

Section: Proton Conductivity Of Composite/cs‐tsia/ceo2mentioning

confidence: 99%

“…2 The perfluorosulfonic polymer membranes such as Nafion made by Dupont are commercially most used in polymer electrolyte membrane water electrolysis (PEMWE). 4,5 Our focus has been to complete the preparation of a series of heteropoly acids (HPAs) and CeO 2 included SPEEK system composite membranes for water electrolysis. 3 Accordingly, nonfluorine polymers like sulfonated polyether ether ketone (SPEEK) are of significant interest due to their low costs and outstanding electrochemical properties.…”

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confidence: 99%

Development and Electrochemical Characterization of Polyether Ether Ketone Composites Including Polyoxometal Tungstosilicic Acid for Water Electrolysis

Kim

Song

Seo

et al. 2018

Bulletin Korean Chem Soc

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“…These shortcomings have catalyzed the search for alternative membrane materials and materials for proton conduction in the electrode (ionomer). One centrally important class of materials considered as an alternative are hydrocarbon polymers [8,9] such as aromatic polyethers [10,11], polyethersulfones [12], polyetherketones [13], polyphenylphosphine oxides [14], polyphenylenes [15], polysulfones [16], and other aromatic main-chain polymers. A particular advantage of hydrocarbon ionomer membranes, compared to PFSA membranes, is the lower gas crossover, leading to a reduction in safety issues, faradaic efficiency losses and radical formation, and consequently, less membrane degradation [17,18].…”

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confidence: 99%

H+-Conducting Aromatic Multiblock Copolymer and Blend Membranes and Their Application in PEM Electrolysis

et al. 2021

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As an alternative to common perfluorosulfonic acid-based polyelectrolytes, we present the synthesis and characterization of proton exchange membranes based on two different concepts: (i) Covalently bound multiblock-co-ionomers with a nanophase-separated structure exhibit tunable properties depending on hydrophilic and hydrophobic components’ ratios. Here, the blocks were synthesized individually via step-growth polycondensation from either partially fluorinated or sulfonated aromatic monomers. (ii) Ionically crosslinked blend membranes of partially fluorinated polybenzimidazole and pyridine side-chain-modified polysulfones combine the hydrophilic component’s high proton conductivities with high mechanical stability established by the hydrophobic components. In addition to the polymer synthesis, membrane preparation, and thorough characterization of the obtained materials, hydrogen permeability is determined using linear sweep voltammetry. Furthermore, initial in situ tests in a PEM electrolysis cell show promising cell performance, which can be increased by optimizing electrodes with regard to binders for the respective membrane material.

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Sulfonated poly(arylene thioether phosphine oxide)s and poly(arylene ether phosphine oxide)s PBI-blend membranes and their performance in SO2 electrolysis

Cited by 13 publications

References 26 publications

Characterizing Voltage Losses in an SO₂Depolarized Electrolyzer Using Sulfonated Polybenzimidazole Membranes

Characterizing Voltage Losses in an SO₂Depolarized Electrolyzer Using Sulfonated Polybenzimidazole Membranes

Development and Electrochemical Characterization of Polyether Ether Ketone Composites Including Polyoxometal Tungstosilicic Acid for Water Electrolysis

H+-Conducting Aromatic Multiblock Copolymer and Blend Membranes and Their Application in PEM Electrolysis

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Sulfonated poly(arylene thioether phosphine oxide)s and poly(arylene ether phosphine oxide)s PBI-blend membranes and their performance in SO2 electrolysis

Cited by 13 publications

References 26 publications

Characterizing Voltage Losses in an SO2Depolarized Electrolyzer Using Sulfonated Polybenzimidazole Membranes

Characterizing Voltage Losses in an SO2Depolarized Electrolyzer Using Sulfonated Polybenzimidazole Membranes

Development and Electrochemical Characterization of Polyether Ether Ketone Composites Including Polyoxometal Tungstosilicic Acid for Water Electrolysis

H+-Conducting Aromatic Multiblock Copolymer and Blend Membranes and Their Application in PEM Electrolysis

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Product

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Characterizing Voltage Losses in an SO₂Depolarized Electrolyzer Using Sulfonated Polybenzimidazole Membranes

Characterizing Voltage Losses in an SO₂Depolarized Electrolyzer Using Sulfonated Polybenzimidazole Membranes