Electrospun Modified Polyketone-Based Anion Exchange Membranes with High Ionic Conductivity and Robust Mechanical Properties

Zhou, Yulong; Bao, Rui‐Ying; Liu, Zhengying; Yang, Ming‐Bo

doi:10.1021/acsaem.1c00727

Cited by 22 publications

(28 citation statements)

References 70 publications

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“…The TMA functional groups are subjected to different degradation mechanisms at high temperatures and alkaline environments, mainly to nucleophilic substitution (S N 2), Ylide formation, and Hofmann elimination. ,,− The degradation process is closely related to the level of hydration. Therefore, the interaction of the TMA head group with OH – and different hydration levels will be analyzed with structures 4, 7, and 8, with λ equal to 0, 2, and 4 respectively, simulating the hydrated condition by explicitly adding water molecules to the system.…”

Section: Resultsmentioning

confidence: 99%

“…In the present work, DFT simulations were carried out on a monomer of the polyamine (PA) − ,− to study the interactions of water molecules and hydroxide anions with a single monomer, eventually extrapolating information on the hydrophilic/hydrophobic nature of the polymer. In addition, the role of functional groups in ion transport and the influence of the hydration level on the degradation of the cationic group are analyzed.…”

Section: Introductionmentioning

confidence: 99%

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Water Uptake in an Anion Exchange Membrane Based on Polyamine: A First-Principles Study

et al. 2022

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An atomistic level study of a single monomer of polyamine interacting with water molecules and hydroxide anions (OH – ) was carried out to investigate the role of the polyamine structure in the hydrated morphology of anion exchange membranes (AEMs) for alkaline fuel cells and its influence on ionic conductivity and chemical stability. DFT calculations were performed to find the ground state of the system, studying the interactions of the solvent species with three different regions of the polymer—the amine functional group, the backbone, and the carbonyl group. The hydrophilic/hydrophobic behavior of each segment was determined, with calculated binding energies and Bader charge analysis providing a more quantitative analysis of the interactions and activation and reaction energies computed to investigate the chemical degradation mechanism. The results show the tendency of both OH – and water molecules to form water clusters in the proximity of the ionized amine group. As such, these regions constitute the preferential pathway for ionic conductivity. Besides, the essential role of the water content is pointed out, not only to enhance conductivity but also to reduce degradation in an alkaline environment. The present work provides a baseline to assess the impact of polymer chemistry on the ionic conductivity of the membrane and acts as the first step for the development of high-performance AEMs and for an improvement of the overall performance of the fuel cell.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Water Uptake in an Anion Exchange Membrane Based on Polyamine: A First-Principles Study

et al. 2022

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“…The process was repeated three times to remove any unreacted amine, and the organic solvent was removed by evaporation. The carbonyl conversion (C CO )-i.e., the molar fraction of 1,4-dicarbonyl units reacted-was determined by elemental analysis (Table S1) using the following equation [25,26]:…”

Section: Polyketone Functionalization With 1-(3-aminopropyl)imidazolementioning

confidence: 99%

Polyketone-Based Anion-Exchange Membranes for Alkaline Water Electrolysis

et al. 2023

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Anion-exchange membranes (AEMs) are involved in a wide range of applications, including fuel cells and water electrolysis. A straightforward method for the preparation of efficient AEMs consists of polymer functionalization with robust anion-exchange sites. In this work, an aliphatic polyketone was functionalized with 1-(3-aminopropyl)imidazole through the Paal–Knorr reaction, with a carbonyl (CCO %) conversion of 33%. The anion-exchange groups were generated by the imidazole quaternization by using two different types of alkyl halides, i.e., 1,4-iodobutane and 1-iodobutane, with the aim of modulating the degree of crosslinking of the derived membrane. All of the membranes were amorphous (Tg ∼ 30 °C), thermally resistant up to 130 °C, and had a minimum Young’s modulus of 372 ± 30 MPa and a maximum of 86 ± 5 % for the elongation at break for the least-crosslinked system. The ionic conductivity of the AEMs was determined at 25 °C by electrochemical impedance spectroscopy (EIS), with a maximum of 9.69 mS/cm, i.e., comparable with that of 9.66 mS/cm measured using a commercially available AEM (Fumasep-PK-130). Future efforts will be directed toward increasing the robustness of these PK-based AEMs to meet all the requirements needed for their application in electrolytic cells.

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“…The derivatives produced in this way still contain PK moieties since the reaction of the PK 1,4-diketone units is statistically random and does not reach completeness even in excess of amine, maintaining some of the original polymer properties. At present, many functionalized polyethylene pyrroles-co-PKs (FPK)with anionic exchange group (ammonium, [12][13][14] pyridinium, [11,15,16] or imidazolium [17,18] ) have been proposed. Their degree of functionalization, or relative number of diketone units converted to pyrrole, which corresponds to the number of functional side chains, can be easily tuned by changing the amine/PK ratio or the reaction conditions (temperature or reaction time).…”

Section: Introductionmentioning

confidence: 99%

Inorganic‐Organic Hybrid Anion Conducting Membranes Based on Ammonium‐Functionalized Polyethylene Pyrrole‐Polyethylene Ketone Copolymer

Alvi

Vezzù

Pagot

et al. 2022

Macro Chemistry & Physics

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New inorganic-organic hybrid anion exchange membranes are produced after incorporation of tantalum oxide into trimethylammonium-functionalized polyethylene pyrrole-co-polyethylene ketone (functionalized polyketone, FPK), obtained by the chemical modification of a polyketone polymer. The influence of tantalum oxide fillers on the properties of the synthesized membranes is investigated. The interaction between inorganic fillers and the polymer chains is studied using Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy (ATR-FTIR). The thermal analysis of the FPK membranes reveals they are thermally stable at up to 250°C. However, the incorporation of the inorganic fillers reduces the thermal stability. Modulated Differential Scanning Calorimetry (MDSC) results indicate that the inclusion of inorganic fillers leads to an increase in crystallinity. This study reports that the properties of the bulk polymer can be tuned by controlling the degree of functionalization and content of inorganic fillers, as confirmed by Near Ambient Pressure X-Ray Photoelectron Spectroscopy (NAP-XPS) studies. Finally, Broadband Electrical Spectroscopy (BES) studies demonstrate that the hybrid membranes are characterized by several polarization phenomena contributing to the overall ion conductivity of the material, which at RT is of 1.46 and 1.61 mS cm −1 for the FPK cast membrane and the hybrid membrane with 5.0 wt.% of Ta 2 O 5 filler, respectively.

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Electrospun Modified Polyketone-Based Anion Exchange Membranes with High Ionic Conductivity and Robust Mechanical Properties

Cited by 22 publications

References 70 publications

Water Uptake in an Anion Exchange Membrane Based on Polyamine: A First-Principles Study

Water Uptake in an Anion Exchange Membrane Based on Polyamine: A First-Principles Study

Polyketone-Based Anion-Exchange Membranes for Alkaline Water Electrolysis

Inorganic‐Organic Hybrid Anion Conducting Membranes Based on Ammonium‐Functionalized Polyethylene Pyrrole‐Polyethylene Ketone Copolymer

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