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| 2. |
- Adebahr, Josefina, et al.
(författare)
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Cation coordination in ion-conducting gels based on PEO-grafted polymers
- 2000
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Ingår i: Solid State Ionics. - 0167-2738. ; 135:1-4, s. 149-154
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Tidskriftsartikel (refereegranskat)abstract
- Ionic conducting polymer gels prepared from PEG-grafted acrylates, ethylene carbonate (EC), dimethyl carbonate (DMC), and LiPF6 are studied by means of infrared and Raman spectroscopy. It is found that the presence of grafted PEO chains substantially changes the coordination of lithium cations from 'cation-solvent' to 'cation-polymer'. Spectroscopic studies show that Li+-PEO coordination is strongly favored in competition with the solvent molecules and dominates completely at ether oxygen to Li-cation ratios (O:Li) of 10:1 and 5:1. At an O:M of 4:1 a solvent-cation interaction arises, in agreement with previously reported MD calculations of a preferred coordination number of 5 in similar systems. The results suggest that the complex interactions which determine long time stability and ionic transport properties can be designed by functionalization of the polymer backbone in PMMA-based gel electrolytes.
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| 3. |
- Aili, David, et al.
(författare)
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Electrode Separators for the Next-Generation Alkaline Water Electrolyzers
- 2023
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Ingår i: ACS Energy Letters. - : American Chemical Society (ACS). - 2380-8195. ; 8:4, s. 1900-1910
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Tidskriftsartikel (refereegranskat)abstract
- Multi-gigawatt-scale hydrogen production by water electrolysis is central in the green transition when it comes to storage of energy and forming the basis for sustainable fuels and materials. Alkaline water electrolysis plays a key role in this context, as the scale of implementation is not limited by the availability of scarce and expensive raw materials. Even though it is a mature technology, the new technological context of the renewable energy system demands more from the systems in terms of higher energy efficiency, enhanced rate capability, as well as dynamic, part-load, and differential pressure operation capability. New electrode separators that can support high currents at small ohmic losses, while effectively suppressing gas crossover, are essential to achieving this. This Focus Review compares the three main development paths that are currently being pursued in the field with the aim to identify the advantages and drawbacks of the different approaches in order to illuminate rational ways forward.
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| 4. |
- Al-Rudainy, Basel, et al.
(författare)
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Impact of lignin content on the properties of hemicellulose hydrogels
- 2019
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Ingår i: Polymers. - : MDPI AG. - 2073-4360. ; 11:1
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Tidskriftsartikel (refereegranskat)abstract
- Hemicellulose is a promising renewable raw material for the production of hydrogels. This polysaccharide exists in large amounts in various waste streams, in which they are usually impure and heavily diluted. Several downstream processing methods can be combined to concentrate and purify the hemicellulose. However, such an approach can be costly; hence, the effect of impurities on the formation and properties of hydrogels must be determined. Lignin usually exists in these waste streams as a major impurity that is also difficult to separate. This compound can darken hydrogels and decrease their swellability and reactivity, as shown in many studies. Other properties and effects of lignin impurities are equally important for the end application of hydrogels and the overall process economy. In this work, we examined the feasibility of producing hydrogels from hemicelluloses that originated from sodium-based spent sulfite liquor. A combination of membrane filtration and anti-solvent precipitation was used to extract and purify various components. The influence of the purity of hemicellulose and the addition of lignosulfonates (emulated impurities in the downstream processing) to the crosslinking reaction mixture on the mechanical, thermal, and chemical properties of hydrogels was determined.
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| 5. |
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| 6. |
- Allushi, Andrit, et al.
(författare)
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Ether-free polyfluorenes tethered with quinuclidinium cations as hydroxide exchange membranes
- 2019
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Ingår i: Journal of Materials Chemistry A. - 2050-7488. ; 7:47, s. 27164-27174
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Tidskriftsartikel (refereegranskat)abstract
- We report on aryl ether-free 2,7-diphenylfluorene-based copolymers tethered with quinuclidinium (Qui) cations via hexyl spacers, prepared through superacid catalyzed Friedel Crafts polycondensation and quaternization reactions. The 2,7-diphenylfluorene monomers were prepared by Suzuki coupling and employed to increase polymer backbone stiffness. Corresponding copolymers and anion-exchange membranes (AEMs) tethered with piperidinium (Pip) and trimethylalkyl ammonium (TMA) cations were prepared as reference materials. At a given water content, the AEM functionalized with Qui cations was the most efficient hydroxide conductor and reached 100 mS cm-1 at 80 °C at an ion exchange capacity of 2.0 mequiv g-1. Moreover, this membrane showed the highest thermal and alkaline stability in the series. 1H NMR analysis of AEMs stored in 2 M aq. NaOH at 90 °C over 672 h revealed the complete absence of ring-opening β-elimination in the bicyclic cage-like Qui structure, and only ~1% β-elimination in the hexyl spacer. In contrast, the Pip cations were found to degrade via β-elimination in both the monocyclic ring structure and the hexyl spacer. Results on the Pip-modified AEM implied that a β-hydrogen in the linear alkyl spacer chain was approximately 4 times more vulnerable to elimination than a β-hydrogen in the 6-membered ring. In addition, all the cations degraded via substitution reactions to some degree, and the total loss of Qui, Pip and TMA cations over the period was estimated to 4, 12 and 9%, respectively. The overall findings demonstrate that the combination of aryl-ether free backbone polymers and Qui cations results in durable and high-performance AEMs suitable for use in alkaline electrochemical energy conversion and storage devices.
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| 7. |
- Allushi, Andrit, et al.
(författare)
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Highly conductive hydroxide exchange membranes containing fluorene-units tethered with dual pairs of quaternary piperidinium cations
- 2021
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Ingår i: Journal of Membrane Science. - : Elsevier BV. - 0376-7388. ; 632
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Tidskriftsartikel (refereegranskat)abstract
- In the pursuit of anion exchange membranes (AEMs) with high alkaline stability and hydroxide conductivity, we have prepared and characterized a series of poly(fluorene alkylene)s in which each fluorene unit was functionalized with dual pairs of quaternary piperidinium cations on flexible alkyl spacer chains. First, ether-free precursor polymers were synthesized in superacid mediated polyhydroxyalkylations of 2,2,2-trifluoroacetophenone, 9,9-dimethyl-2,7-diphenyl-9H-fluorene, and different amounts of 2,7-dibromo-9,9-bis(6-bromohexyl)-fluorene to regulate the degree of bromoalkylation. Subsequently, the bromoalkyl side chains were utilized to introduce bis-piperidinium (bisPip) cations via Menshutkin reactions. These materials formed transparent and mechanically strong AEMs upon casting. At 80 °C, the hydroxide conductivity of bisPip AEMs reached 85 and 150 mS cm–1 at ion-exchange capacities (IECs) of 2.0 and 2.8 mequiv g–1, respectively. Moreover, the bisPip AEMs showed high alkaline stability with an ionic loss of merely 6% following immersion in 5 M aq. NaOH solution for a period of 168 h at IEC = 2.8 mequiv g–1. Under these conditions, 1H NMR data indicated that a β-hydrogen in an alkyl spacer chain was about 8 times more susceptible to attacks by hydroxide ions than a β-hydrogen in a piperidinium ring. In comparison, corresponding AEMs with fluorene units functionalized with monoPip cations (i.e., a single pair of piperidinium cations per fluorine unit) showed lower conductivity and alkaline stability under the same conditions, demonstrating the advantage of locally concentrating the cations in the polymer structure by employingbisPip side chains.
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| 8. |
- Allushi, Andrit, et al.
(författare)
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Hydroxide conducting BAB triblock copolymers tailored for durable high-performance anion exchange membranes
- 2023
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Ingår i: Materials Advances. - 2633-5409. ; 4:17, s. 3733-3745
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Tidskriftsartikel (refereegranskat)abstract
- Well-designed block copolymers with a controlled co-continuous microphase morphology can be applied as efficient anion exchange membranes (AEMs) for fuel cells and water electrolyzers. In the present work, we have prepared and studied a series of BAB triblock copolymers consisting of a central cationic polyfluorene A block with flanking hydrophobic polystyrene B blocks, where the fluorene units of the A block carried double pairs of piperidinium cations via flexible hexyl spacer chains. First, a polyfluorene tethered with bromohexyl chains was prepared by superacid-mediated polyhydroxyalkylation, and then modified to produce a bi-directional macroinitiator for atom transfer radical polymerization (ATRP). Next, ATRP of styrene was carried out to form BAB triblock copolymers with different lengths of the B blocks. Finally, the polyfluorene block was densely functionalized with piperidinium cations by Menshutkin reactions. Small angle X-ray scattering of block copolymer AEMs indicated the presence of both block copolymer phase domains (d~15 nm) and ionic clusters (d~6 nm). Atomic force microscopy showed clearly phase-separated morphologies with seemingly well-connected hydrophilic nanophase domains for ion transport. The AEMs reached hydroxide conductivities up to 161 mS cm-1 at 80 ºC. Moreover, the AEMs decomposed only above 250 °C and possessed excellent alkaline stability with no degradation detected by 1H NMR analysis after storage in 2 M aq. NaOH, at 90 °C during 672 h. Notably, the current block copolymer AEMs showed higher alkaline stability and hydroxide conductivity compared to AEMs based on corresponding statistical copolymers.
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| 9. |
- Allushi, Andrit, et al.
(författare)
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Polyfluorenes Bearing N,N-Dimethylpiperidinium Cations on Short Spacers for Durable Anion Exchange Membranes
- 2023
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Ingår i: Macromolecules. - : American Chemical Society (ACS). - 0024-9297 .- 1520-5835. ; 56:3, s. 1165-1176
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Tidskriftsartikel (refereegranskat)abstract
- Alicyclic quaternary ammonium cations having all the β-protons in a strain-free ring structure are in general highly base resistant, and are thus very attractive to employ for anion exchange membrane (AEM) applications. However, tethering cations such as N,N-dimethylpiperidinium (DMP) to polymer backbones without introducing any weak links is quite challenging. In the present study, we have attached pairs of piperidine rings in their 4-position to fluorene and 2,7-diphenylfluorene via methylene bridges using straightforward SN2 reactions. These fluorenes were subsequently utilized as monomers in polyhydroxyalkylations to prepare poly(fluorene alkylene)s with different contents of the piperidine groups. AEMs were cast after quaternizing the piperidine groups to introduce DMP and spirocyclic 6-azonia-spiro-[5,5]undecane-6-ium (ASU) cations, respectively. The AEMs reached very high hydroxide ion conductivities, 100-156 mS cm-1 at 80 ºC, in the ion exchange capacity (IEC) range 1.8-2.4 mequiv. g-1. X-ray scattering showed ionomer peaks indicating ionic clustering with a characteristic distance d = 2.0-2.9 nm depending on IEC. The AEMs displayed high thermal stability, up to ~250 ºC, and 1H NMR data indicated no degradation after storage in 5 M aq. NaOH during 168 h at 90 ºC. However, degradation started under very severe conditions (10 M, 90 °C) with ~75% of the total ionic loss in all the AEMs assigned to Hofmann β-elimination. The overall results show that fluorene-based AEMs carrying DMP and ASU cations via methylene bridges display an attractive combination of ionic phase separation, thermal and chemical stability, and hydroxide conductivity.
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