RESUMEN
Anion exchange membranes (AEMs) based on hydroxide-conducting polymers (HCPs) are a key component for anion-based electrochemical energy technology such as fuel cells, electrolyzers, and advanced batteries. Although these alkaline electrochemical applications offer a promising alternative to acidic proton exchange membrane electrochemical devices, access to alkaline-stable and high-performing polymer electrolyte materials has remained elusive until now. Despite vigorous research of AEM polymer design, literature examples of high-performance polymers with good alkaline stability at an elevated temperature are uncommon. Traditional aromatic polymers used in AEM applications contain a heteroatomic backbone linkage, such as an aryl ether bond, which is prone to degradation via nucleophilic attack by hydroxide ion. In this Account, we highlight some of the progress our group has made in the development of advanced HCPs for applications in AEMs and electrode ionomers. We propose that a synthetic polymer design with an all C-C bond backbone and a flexible chain-tethered quaternary ammonium group provides an effective solution to the problem of alkaline stability. Because of the critical demand for such a polymer system, we have established new synthetic strategies for polymer functionalization and polycondensation using an acid catalyst. The first approach is to graft a cationic tethered alkyl group to pre-existing, commercially available styrene-based block copolymers. The second approach is to synthesize high-molecular-weight aromatic backbone polymers using acid-catalyzed polycondensation of arene monomers and a functionalized trifluoromethyl ketone substrate. Both strategies involve a simple two-step reaction process and avoid the use of expensive metal-based catalysts and toxic chemicals, thereby making the synthetic processes easily scalable to large industrial quantities. Both polymer systems were found to have excellent alkaline stability, confirmed by the preservation of ion exchange capacity and ion conductivity of the membrane after an alkaline test under conditions of 1 M NaOH at 80-95 °C. In addition, the advantage of good solvent processability and convenient scalability of the reaction process generates considerable interest in these polymers as commercial standard AEM candidates. AEM fuel cell and electrolyzer tests of some of the developed polymer membranes showed excellent performance, suggesting that this new class of HCPs opens a new avenue to electrochemical devices with real-world applications.
RESUMEN
The compositional dependence of the open-circuit voltage (Voc) in ternary blend bulk heterojunction (BHJ) solar cells is correlated with the miscibility of polymers, which may be influenced by a number of attributes, including crystallinity, the random copolymer effect, or surface energy. Four ternary blend systems featuring poly(3-hexylthiophene-co-3-(2-ethylhexyl)thiophene) (P3HT75-co-EHT25), poly(3-hexylthiophene-co-(hexyl-3-carboxylate)), herein referred to as poly(3-hexylthiophene-co-3-hexylesterthiophene) (P3HT50-co-3HET50), poly(3-hexylthiophene-thiophene-diketopyrrolopyrrole) (P3HTT-DPP-10%), and an analog of P3HTT-DPP-10% with 40% of 3-hexylthiophene exchanged for 2-(2-methoxyethoxy)ethylthiophen-2-yl (3MEO-T) (featuring an electronically decoupled oligoether side-chain), referred to as P3HTTDPP-MEO40%, are explored in this work. All four polymers are semicrystalline and rich in rr-P3HT content and perform well in binary devices with PC61BM. Except for P3HTTDPP-MEO40%, all polymers exhibit similar surface energies (â¼21-22 mN/m). P3HTTDPP-MEO40% exhibits an elevated surface energy of around 26 mN/m. As a result, despite the similar optoelectronic properties and binary solar cell performance of P3HTTDPP-MEO40% compared to P3HTT-DPP-10%, the former exhibits a pinned Voc in two different sets of ternary blend devices. This is a stark contrast to previous rr-P3HT-based systems and demonstrates that surface energy, and its influence on miscibility, plays a critical role in the formation of organic alloys and can supersede the influence of crystallinity, the random copolymer effect, similar backbone structures, and HOMO/LUMO considerations. Therefore, we confirm surface energy compatibility as a figure-of-merit for predicting the compositional dependence of the Voc in ternary blend solar cells and highlight the importance of polymer miscibility in organic alloy formation.
RESUMEN
Alkyl solubilizing side chains on conjugated polymers can serve as a handle for modifying polymer properties. Recently, oligo-ether and semifluoro alkyl side chains were utilized to tune the surface energy of random P3HT-based polymers without changing the optical and electronic properties. Here, this method is applied to semi-random poly(3-hexylthiophene-thiophene-diketopyrrolopyrrole) (P3HTT-DPP) and the subsequent polymer device, optical, electronic, structural, and thermal properties are characterized. P3HTMETT-DPP, bearing oligo-ether side chains, exhibited higher crystallinity, closer lamellar packing, and lower temperature thermal transitions. P3HTFHTT-DPP, featuring semifluoro alkyl side chains, presented reduced crystallinity, greater lamellar packing distances, and higher temperature thermal transitions. P3HTMETT-DPP performed similarly to P3HTT-DPP under identical processing conditions, whereas P3HTFHTT-DPP had greatly reduced JSC due to lower polymer concentration necessitated by solubility.
RESUMEN
Recent work has pointed to polymer miscibility and surface energy as key figures of merit in the formation of organic alloys and synergistic behavior between components in ternary blend solar cells. Here, we present a simple model system and first report of poly(3-hexylthiophene)-based random copolymers featuring either a semifluoroalkyl (P3HT-co-FHT) or oligoether (P3HT-co-MET) side chain, prepared via Stille polycondensation. Water drop contact angle measurements demonstrated that P3HT-co-FHT polymers reached a minimum surface energy of 14.2 mN/m at 50% composition of comonomers, while in contrast, P3HT-co-MET polymers increased as high as 27.0 mN/m at 50% composition, compared to P3HT at 19.9 mN/m. Importantly, the surface energy of the copolymers was found to vary regularly with comonomer composition and exhibited fine-tuning. Optical and electronic properties of the polymers are found to be composition independent as determined by UV-vis and CV measurements; HOMO energy levels ranged from 5.25 to 5.30 eV; and optical band gaps all measured 1.9 eV. Following this model, surface energy modification of state-of-the-art polymers, without altering desirable electronic and optical properties, is proposed as a useful tool in identifying and exploiting more alloying polymer pairs for ternary blend solar cells.
RESUMEN
In an effort to broaden the absorption of conjugated polymers, atomistic bandgap control was applied to the semi-random polymer architecture. Here, we report the physical properties of semi-random polyselenophenes as compared to analogous polythiophenes. In order to examine the effect of the selenium heteroatom on the optical properties of the polymers, UV-vis spectra were studied and it was found that all polyselenophenes exhibit lower bandgaps and higher absorption coefficients in thin films. Further, differential scanning calorimetry and grazing incidence x-ray diffraction results indicate that semi-random polyselenophenes are semicrystalline polymers and their (100) interchain distances are shorter than in the case of semi-random polythiophenes, which may be responsible for higher absorption coefficients. To probe the effect of the selenium heteroatom on the nano-organization of these polymers and their blends with PC61BM, thin films were studied by transmission electron microscopy (TEM). The TEM images show a segregation between more densely packed areas from less densely packed areas in the pristine polymer films, which is more pronounced for polyselenophenes than for polythiophenes. The blends of polyselenophenes with PC61BM do not show the well-defined segregation observed for the polythiophene analogues. However, the broadened and extended absorption of semi-random polyselenophenes translates into an extended photocurrent response in the photovoltaic devices, as evidenced by external quantum efficiency measurements.
