Ternary Polymer Research Articles

19.28% Efficiency and Stable Polymer Solar Cells Enabled by Introducing an NIR‐Absorbing Guest Acceptor

AbstractHere, a near‐infrared (NIR)‐absorbing small‐molecule acceptor (SMA) Y‐SeNF with strong intermolecular interaction and crystallinity is developed by combining selenophene‐fused core with naphthalene‐containing end‐group, and then as a custom‐tailor guest acceptor is incorporated into the binary PM6:L8‐BO host system. Y‐SeNF shows a 65 nm red‐shifted absorption compared to L8‐BO. Thanks to the strong crystallinity and intermolecular interaction of Y‐SeNF, the morphology of PM6:L8‐BO:Y‐SeNF can be precisely regulated by introducing Y‐SeNF, achieving improved charge‐transporting and suppressed non‐radiative energy loss. Consequently, ternary polymer solar cells (PSCs) offer an impressive device efficiency of 19.28% with both high photovoltage (0.873 V) and photocurrent (27.88 mA cm−2), which is one of the highest efficiencies in reported single‐junction PSCs. Notably, ternary PSC has excellent stability under maximum‐power‐point tracking for even over 200 h, which is better than its parental binary devices. The study provides a novel strategy to construct NIR‐absorbing SMA for efficient and stable PSCs toward practical applications.

Fully bio-based ternary polymer blends: structural characterization and mechanical behavior

In this work, ternary immiscible blends based on poly (lactic acid) (PLA) as major phase and polybutylene succinate (PBS) and poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBHH) as minor phases were prepared through melt blending, aiming at obtaining fully biobased materials with enhanced ductility and toughness as compared to the inherently brittle matrix. Thermodynamic considerations based on the calculation of the interfacial tensions predicted the achievement of a partial encapsulation between the domains of the two minor components embedded in the PLA matrix. The rheological characterization revealed higher melt viscosity and elasticity for all the ternary blends as compared to the PLA matrix and a growing level of interfacial interactions between the different phases when increasing amounts of PBS are incorporated. This last was confirmed through morphological observations, which allowed demonstrating the achievement of an improved homogeneous microstructure for the blends containing 30 and 40 wt% of PBS, notwithstanding the relatively good interfacial adhesion obtained in all the explored materials. The combined effect of the strong established interfacial interactions and of the uniform morphology resulted in the obtainment of dramatic increments of ductility, tensile toughness and impact strength for all formulated ternary blends as compared to the PLA matrix, and especially for those containing 30 or 40 wt% of PBS, while maintaining satisfactory levels of stiffness and tensile strength.

One-pot synthesis of dynamically cross-linked polymers for serum-resistant nucleic acid delivery.

Cationic polymers used for nucleic acid delivery often suffer from complicated syntheses, undesired intracellular cargo release and low serum stability. Herein, a series of ternary polymers were synthesized via facile green chemistry to achieve efficient plasmid DNA and mRNA delivery in serum. During the one-pot synthesis of the ternary polymer, acetylphenylboric acid (APBA), polyphenol and low-molecular weight polyethyleneimine (PEI 1.8k) were dynamically cross-linked with each other due to formation of an imine between PEI 1.8k and APBA and formation of a boronate ester between APBA and polyphenol. Series of polyphenols, including ellagic acid (EA), epigallocatechin gallate (EGCG), nordihydroguaiaretic acid (NDGA), rutin (RT) and rosmarinic acid (RA), and APBA molecules, including 2-acetylphenylboric acid (2-APBA), 3-acetylphenylboric acid (3-APBA) and 4-acetylphenylboric acid (4-APBA), were screened and the best-performing ternary polymer, 2-PEI-RT, constructed from RT and 2-APBA, was identified. The ternary polymer featured efficient DNA condensation to favor cellular internalization, and the acidic environment in endolysosomes triggered effective degradation of the polymer to promote cargo release. Thus, 2-PEI-RT showed robust plasmid DNA transfection efficiencies in various tumor cells in serum, outperforming the commercial reagent PEI 25k by 1-3 orders of magnitude. Moreover, 2-PEI-RT mediated efficient cytosolic delivery of Cas9-mRNA/sgRNA to enable pronounced CRISPR-Cas9 genome editing in vitro. Such a facile and robust platform holds great potential for non-viral nucleic acid delivery and gene therapy.

An ionic liquid- and PEO-based ternary polymer electrolyte for lithium metal batteries: an advanced processing solvent-free approach for solid electrolyte processing.

A processing solvent-free manufacturing process for cross-linked ternary solid polymer electrolytes (TSPEs) is presented. Ternary electrolytes (PEODA, Pyr14TFSI, LiTFSI) with high ionic conductivities of >1 mS cm-1 are obtained. It is shown that an increased LiTFSI content in the formulation (10 wt% to 30 wt%) decreases the risk of short-circuits by HSAL significantly. The practical areal capacity increases by more than a factor of 20 from 0.42 mA h cm-2 to 8.80 mA h cm-2 before a short-circuit occurs. With increasing Pyr14TFSI content, the temperature dependency of the ionic conductivity changes from Vogel-Fulcher-Tammann to Arrhenius behavior, leading to activation energies for the ion conduction of 0.23 eV. In addition, high Coulombic efficiencies of 93% in Cu‖Li cells and limiting current densities of 0.46 mA cm-2 in Li‖Li cells were obtained. Due to a temperature stability of >300 °C the electrolyte guarantees high safety in a broad window of conditions. In LFP‖Li cells, a high discharge capacity of 150 mA h g-1 after 100 cycles at 60 °C was achieved.

Correlating miscibility, mechanical parameters, and stability of ternary polymer blends for high-performance solar cells

The established miscibility–function relationships are helpful to predict mechanical properties and stability in organic photovoltaic devices based on multicomponent systems.

Single junction binary and ternary polymer solar cells-based D–A structured copolymer with low lying HOMO energy level and two nonfullerene acceptors

The power conversion efficiency of the ternary PSCs (16.32%) is higher than that for binary counterparts, i.e., 13.16% and 12.62% for P(DTB-BDD):DBTBT-IC and P(DTB-BDD):Y6, respectively.

Highly-concentrated bis(fluorosulfonyl)imide-based ternary gel polymer electrolytes for high-voltage lithium metal batteries

Polymer electrolytes (PEs) have arisen as the most promising candidates for being used in rechargeable lithium metal batteries (LMBs). However, classic gel polymer electrolytes (GPEs) with volatile plasticizers show poor inherent safety, despite their higher ionic conductivities vs. dry PE systems, which largely hampers the practical deployment of GPE-based LMBs. Herein, we report the electrochemical performances of a highly-concentrated bis(fluorosulfonyl)imide (FSI)-based ternary gel polymer electrolyte (TGPE) comprising a plasticized polymerized ionic liquid as polymer scaffold. The as-prepared FSI-TGPEs show high lithium-ion conductivities at room temperature, wide electrochemical stability both at oxidative and reductive potentials, and superior compatibility with lithium metal electrode. These unique properties of FSI-TGPE enable stable Li plating and stripping processes, as well as high discharge capacity of a Li||Li(Ni0.6Mn0.2Co0.2)O2 cell at ambient temperatures. The present work offers not only safe and highly conductive PEs but also a better understanding on the determining role of FSI− anions in high-energy LMBs.

Effect of UV-Light Irradiation on Charge-Accumulation States in PTzBT Polymer Solar Cells

Ternary polymer solar cells based on a polymer PTzBT have received a lot of attention because their power conversion efficiency (PCE) and thermal stability have been greatly improved by adding a small amount of an oligomer ITIC. However, the charge-accumulation states of the PTzBT ternary polymer solar cells have not yet been completely clarified. Here, we report electron spin resonance (ESR) spectroscopy of the PTzBT ternary polymer solar cells to investigate the charge-accumulation states from a microscopic viewpoint with examining the effect of UV-light irradiation. We observed a slight increase in the ESR intensity of the PTzBT cells and layered film samples under simulated solar irradiation with a UV-cut filter. Multiple signals were observed in the PTzBT cells under solar irradiation when the UV-cut filter was removed. Interestingly, no decrease was observed in the ESR signal of ZnO under solar irradiation with the UV-cut filter, although holes in ZnO in the PTzBT cells are known to decrease under solar irradiation. These findings will contribute to a deep understanding of the material properties of polymer solar cells.

Phase behavior of π-conjugated polymer and non-fullerene acceptor (PTB7-Th:ITIC) solutions and blends

Phase diagrams of ternary π-bonded polymer (PTB7-Th) solutions were constructed as a function of molecular weight, temperature, and electron acceptor species (ITIC, PC61BM and PC71BM). For this purpose, the Flory–Huggins lattice theory was employed with a constant χ interaction parameter, describing a binodal, spinodal, tie line, and critical point. Then, the morphologies of the blends composed of highly disordered PTB7-Th and crystallizable ITIC were investigated by atomic force microscopy. Subsequently, the surface polarities of the PTB7-Th:ITIC thin films were examined by water contact-angle goniometer, exhibiting a transition at the composition of ~ 60 ± 10 wt.% ITIC. Furthermore, X-ray diffraction indicated the presence of ITIC’s crystallites at ≥ 70 wt.% ITIC. Hence, the PTB7-Th:ITIC system was observed to undergo a phase transition at ~ 60–70 wt.% ITIC.

Preparation of lightweight and high‐strength polypropylene‐based ternary conductive polymer foams by in situ microfiber reinforcement

AbstractConductive polymer composites (CPCs) have demonstrated significant potential in the aerospace, electronics, and communications industries. In this study, polypropylene (PP)/multiwalled carbon nanotubes (MWCNTs) binary composites and in situ fiber reinforced multicomposites made from PP/MWCNTs were fabricated by microcellular injection molding. In addition to crystallization behavior, foam morphology, mechanical properties, dielectric properties, and electromagnetic shielding properties of the composites were analyzed. According to the results, microporous structures can facilitate the distribution of conductive fillers, thereby enhancing the electromagnetic shielding performance and mechanical properties of the composite. In situ microfiber networks display a heterogeneous nucleation effect, resulting in an increase in foam density, which improves composite performance. In situ fiber‐reinforced microporous multicomposites are capable of exhibiting higher elongation at break and electromagnetic shielding properties than binary systems, and the multicomposites can achieve greater electromagnetic shielding effectiveness (SE) with fewer conductive fillers. Ultimately, fiber‐reinforced microporous composites with an elongation at break of 194.40%, an electromagnetic shielding effect of >20 dB, and an absorption mechanism are produced. A feasible method is presented in this study for preparing CPCs that produce light weight, excellent mechanical properties, and high electromagnetic SE at low filler levels.

A polymer sponge with dual absorption of mechanical and electromagnetic energy

Polyaniline, a modified conductive polymer, has been widely studied in the field of electromagnetic (EM) wave absorption due to its excellent dielectric and conductive properties. However, it has limited applications due to its hard molding and processing, and poor mechanical stability. In this study, ice crystals with rapid directional growth were used as templates for polymerization to obtain polymer precursors with directional channels, and then ternary polymer sponges with oriented pore channels were designed and synthesized using a secondary template method. The Poisson's ratio of the study material reaches −1.52 and it absorbs 5.1 mJ/cm3 energy in a single compression cycle at 25% longitudinal strain. Also, the material has more than 90% absorption efficiency for X-band EM waves at a thickness of 4 mm. The flexibility of polymer molecular chains and the arrangement of oriented pores are the reasons for the negative Poisson's ratio property of the material, while the key to the loss of EM energy in the absorption process is the conversion of quinone bipolaron to monopolaron structure. Due to its large-scale green preparation with ice crystal as the template, this lightweight and robust material system are ideal for absorbing EM waves under extreme conditions.

Influence of Dopant Concentration and Annealing on Binary and Ternary Polymer Blends for Active Materials in OLEDs.

Obtaining white light from organic LEDs is a considerable challenge and, to realize white light emission, many studies have been conducted, primarily addressing two- or three-color blend systems as a promising strategy. In this work, pristine films, grown by spin coating, consisting of commercial blue Poly(9,9-di-n-octylfluorenyl-2,7-diyl) (PFO), green Poly(9,9-dioctylfluorene-alt-benzothiadiazole) (F8BT), and red spiro-copolymer (SPR) light-emitting materials, were studied as reference materials. Afterward, binary (SPR doped in host PFO) and ternary (SPR and F8BT doped in host PFO) thin films were successfully prepared with various ratios. The characterization of the as-grown and thermally-treated blend films was focused on their optical and photophysical properties. After, the fabrication of OLED devices on glass substrates was carried out for the evaluation of a blend's composition and annealing in terms of the devices' electrical characteristics and electro-emission properties in order to achieve white light emission. Their analysis provided insights into the energy transfer mechanisms between the constituent materials, which were correlated to host-guest interactions as well as to the structural changes originated by thermal treatment, leading to the crystallization of PFO. Finally, the OLEDs based on ternary blends approach the white light emission with (x, y) of (0.272, 0.346). These fabricated devices also exhibit turn-on voltages as low as 3 V, accompanied by remarkable luminance values above 3000 cd/m2.

Coordinating Anions “to the Rescue” of the Lithium Ion Mobility in Ternary Solid Polymer Electrolytes Plasticized With Ionic Liquids

AbstractLithium salts with low coordinating anions such as bis(trifluoromethanesulfonyl)imide (TFSI) have been the state‐of‐the‐art for polyethylene oxide (PEO)‐based “dry” polymer electrolytes for 3 decades. Plasticizing PEO with TFSI‐based ionic liquids (ILs) to form ternary solid polymer electrolytes (TSPEs) increases conductivity and Li+ diffusivity. However, the Li+ transport mechanism is unaffected compared to their “dry” counterparts and is essentially coupled to the dynamics of the polymer host matrix, which limits Li+ transport improvement. Thus, a paradigm shift is hereby suggested: the utilization of more coordinating anions such as trifluoromethanesulfonyl‐N‐cyanoamide (TFSAM), able to compete with PEO for Li+ solvation, to accelerate the Li+ transport and reach a higher Li+ transference number. The Li–TFSAM interaction in binary and ternary TFSAM‐based electrolytes is probed by experimental methods and discussed in the context of recent computational results. In PEO‐based TSPEs, TFSAM drastically accelerates the Li+ transport (increases Li+ transference number by a factor 6 and the Li+ conductivity by 2–3) and computer simulations reveal that lithium dynamics are effectively re‐coupled from polymer to anion dynamics. Last, this concept of coordinating anions in TSPEs is successfully applied in LFP||Li metal cells leading to enhanced capacity retention (86% after 300 cycles) and an improved rate performance at 2C.

Influence of PCL and PHBV on PLLA Thermal and Mechanical Properties in Binary and Ternary Polymer Blends.

PLLA, PCL and PHBV are aliphatic polyesters which have been researched and used in a wide range of medical devices, and all three have advantages and disadvantages for specific applications. Blending of these materials is an attractive way to make a material which overcomes the limitations of the individual polymers. Both PCL and PHBV have been evaluated in polymer blends with PLLA in order to provide enhanced properties for specific applications. This paper explores the use of PCL and PHBV together with PLLA in ternary blends with assessment of the thermal, mechanical and processing properties of the resultant polymer blends, with the aim of producing new biomaterials for orthopaedic applications. DSC characterisation is used to demonstrate that the materials can be effectively blended. Blending PCL and PHBV in concentrations of 5-10% with PLLA produces materials with average modulus improved by up to 25%, average strength improved by up to 50% and average elongation at break improved by 4000%, depending on the concentrations of each polymer used. PHBV impacts most on the modulus and strength of the blends, whilst PCL has a greater impact on creep behaviour and viscosity. Blending PCL and PHBV with PLLA offers an effective approach to the development of new polyester-based biomaterials with combinations of mechanical properties which cannot be provided by any of the materials individually.

Unprecedented Efficiency Increase in a Ternary Polymer Solar Cell Exhibiting Polymer-Mediated Polymorphism of a Non-Fullerene Acceptor

Unprecedented Efficiency Increase in a Ternary Polymer Solar Cell Exhibiting Polymer-Mediated Polymorphism of a Non-Fullerene Acceptor

Effect of Cationic Groups on the Selectivity of Ternary Antimicrobial Polymers

Back Cover: In article 2200377, Cyrille Boyer and co-workers show the antimicrobial polymers as a promising approach to combat multidrugresistant pathogens. A library of 31 amphiphilic ternary polymers containing different cationic groups, including primary amine, guanidine, and sulfonium groups, is prepared to investigate the impact of cationic groups on antimicrobial activity and cytotoxicity against mammalian cells.

How to Improve Solubility and Dissolution of Irbesartan by Fabricating Ternary Solid Dispersions: Optimization and In-Vitro Characterization

The purpose of this study is to improve the solubility and dissolution of a poorly soluble drug, Irbesartan, using solid dispersion techniques. For that purpose, different polymers such as Soluplus®, Kollidon® VA 64, Kolliphor® P 407, and Polyinylpyrrolidone (PVP-K30) were used as carriers at different concentrations to prepare solid dispersion formulations through the solvent evaporation method. In order to prepare binary dispersion formulations, Soluplus® and Kollidon® VA 64 were used at drug: polymer ratios of 1:1, 1:2, 1:3, and 1:4 (w/w). Saturation solubility of the drug in the presence of used carriers was performed to investigate the quantitative increase in solubility. Dissolution studies were performed to explore the drug release behavior from the prepared dispersions. Additionally, the characterization of the prepared formulations was carried out by performing DSC, SEM, XRD, and FTIR studies. The results revealed that among binary systems, K4 formulation (Drug: Kollidon® VA 64 at ratio of 1:4 w/w) exhibited optimal performance in terms of increased solubility, drug release, and other investigated parameters. Furthermore, ternary dispersion formulations of the optimized binary formulation were prepared with two more polymers, Kolliphor® P 407 and Polyvinylpyrrolidone (PVP-K30), at (Drug: Kollidon® VA 64:ternary polymer) ratios of 1:4:1, 1:4:2, and 1:4:3 (w/w). The results showed that KPVP (TD3) exhibited the highest increase in solubility, as well as dissolution rate, among ternary solid dispersion formulations. Results of solubility enhancement by ternary solid dispersion formulations were also supported by FTIR, DSC, XRD, and SEM analysis. Conclusively, it was found that the ternary solid dispersion-based systems were more effective compared to the binary combinations in improving solubility as well as dissolution of a poorly soluble drug (Irbesartan).

Synergistic removal of U(VI) from aqueous solution by TAC material: Adsorption behavior and mechanism

The adsorption and recovery of uranium from wastewater is of positive significance to the development of nuclear industry and environmental remediation. The ternary polymer (PZS-co-TA) was prepared from hexachlorocyclotriphosphazene (HCCP), 4,4-sulfonyldiphenol (BPS) and tannic acid (TA) under ultrasonic. TAC was then obtained after carbonization under high temperature from PZS-co-TA. The structure and performance of TAC were analyzed using SEM, EDS, FT-IR, XRD, Raman, BET and TG. The adsorption capacity of TAC for uranium under different static adsorption conditions was investigated. The adsorption process was more consistent with pseudo-second-order model. The maximum adsorption capacity calculated by non-linear Langmuir model was 492.5 mg/g at pH 5.5. The thermodynamic values suggested that the adsorption process was spontaneous and endothermic. Moreover, after five cycles of adsorption-desorption tests, TAC remained effective at adsorbing uranium, implying the introducing of TA to the precursor (PZS-co-TA) could enhance the adsorption capacity for uranium.

Fabrication of binary to quaternary PVDF based flexible composite films and ultrathin sandwich structured quaternary PVDF/CB/g-C3N4/BaFe11.5Al0.5O19 composite films for efficient EMI shielding performance

This work reports the facile fabrication of binary, ternary, and quaternary polymer composite films using combinations of Polyvinylidene fluoride (PVDF), Carbon Black (CB), Graphitic carbon nitride (g-C3N4), and Aluminum doped Barium hexaferrite (BaFe11.5Al0.5O19) nanoplatelets for application as EMI shielding materials at X-band frequency. The excellent total EMI-SE of 47.39 dB in X-band for ultra-small thickness of 0.193 mm was observed for the quaternary PVDF/CB/g-C3N4/BaFe11.5Al0.5O19 composite film. The quaternary composite film was further hot pressed into sandwich-structured two-layer and three-layer composite films. The sandwich and/or multi-layered structure of the PVDF/CB/g-C3N4/BaFe11.5Al0.5O19 composite film improved the EMI shielding performance through multiple reflection loss. With the addition of intact conduction of fillers and multiple-reflection-absorption effect, the multi-layered composite structure attained the best shielding efficiency (SE) of 64.54 dB.

Enhanced Photovoltaic Performance of Benzothiadiazole‐Based Polymers by Controlling their Backbone Planarity for Organic Solar Cells

AbstractHere, a new synthetic strategy for converting low‐energy benzo[c][1,2,5]thiadiazole (BT)‐based polymers into efficient polymeric donors for non‐fullerene acceptor‐based organic solar cells (NFA–OSCs) is demonstrated. A highly planar 5,6‐difluoro‐benzo[c][1,2,5]thiadiazole (ffBT)‐based alternating polymer, P1, comprising of electron‐rich 4,8‐bis(5‐(2‐ethylhexyl)thiophen‐2‐yl)benzo[1,2‐b:4,5‐b']dithiophene (BDTT) and strong electron‐deficient 5,6‐difluoro‐4,7‐bis(4‐octylthiophen‐2‐yl)benzo[c][1,2,5]thiadiazole (DTffBT) units is prepared. Additionally, two ternary polymers, P2 and P3, are preparedby replacing 25% and 50% of the DTffBT unit on the P1 backbone with a weak electron‐deficient 2,5‐dioctyl‐4,6‐di(thiophen‐2‐yl)pyrrolo[3,4‐c]pyrrole‐1,3(2H,5H)‐dione (DTPPD) unit, which has a twisted but well‐controlled wavy backbone. The properties of the resulting polymers, P1–P3, are investigated to understand the effects of changing the planarity and curvature of the backbone of the BT‐based polymers. Notably, increasing the concentration of the DTPPD unit on P1 results in ablue‐shift in absorption band and relatively deep energy levels. Further, the π–π stacking of the polymers is decreased by increasing the amount of DTPPD units on P1. The NFA–OSCs fabricated using P1–P3 as the electron donor afford maximum power conversion efficiencies (PCE) of 2.46%, 4.52%, and 7.54%, respectively. Overall, the photovoltaic performance of the BT‐based polymers is significantly improved by lowering their planarity and/or changing their backbone curvature.