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At least 577 records · Page 32

Consequences of utilizing a redox-active polymeric binder in Li-ion batteries

Development of new polymeric binders can help enable the use of silicon-rich anodes in Li-ion batteries, by providing stronger adhesion to the active material particles. The compositional features that improve interfacial interactions and mechanical properties can often impart electronic conductivity and redox activity to these polymers, which are generally seen as beneficial to cell performance. Alternatively, it is also possible that the addition of charge-transferring centers to the electrode can accelerate cell degradation. Here, we use an aromatic polyimide (∼320 mA h/g of reversible capacity) to explore how a redox-active conductive polymer can affect cell performance. We demonstrate that the lithiated polymer is less stable than the traditional binders upon storage, leading to increased rates of calendar aging. Furthermore, we determine that the adhesion properties of the polymer deteriorate upon repeated cycling, to an extent that is proportional to the degree of delithiation of the binder. More critically, we establish that progressive degradation of the redox behavior of the polymer leads to the release of “extra” Li + into the cell, which can give the false perception of good performance even under conditions of poor stability. In conclusion, our work suggests that redox-active conductive binders can sometimes be detrimental to cell performance, and that works evaluating new polymers must include careful experimental validation under realistic conditions.

25 ENERGY STORAGE↗

Anionic multiblock copolymer membrane based on vinyl addition polymerization of norbornenes: Applications in anion-exchange membrane fuel cells

Stable, non-hydrolysable, hydroxide-conducting polymers are of interest for electrochemical devices such as fuel cells, electrolyzers and flow-batteries. In this study, a series of tetrablock copolymers containing an all-hydrocarbon backbone were synthesized. The synthesis is based on vinyl addition polymerization of norbornene using (η 3 -allyl)Pd( i Pr 3 P)Cl as the catalyst and lithium tetrakis(pentafluorophenyl)-borate·(2.5Et 2 O) (Li[FABA]) as the activator. The tetrablock polymers were cast into membranes with an ion-exchange capacity (IEC) between 1.55 and 2.60 milliequivalents per gram (meq/g). The number of bound and unbound water molecules per ion pair was measured and correlated with conductivity. The membrane with the highest IEC (2.60 meq/g) had 10.6 unbound (i.e. free) and 17.9 bound water molecules per ion pair within the polymer. The presence of excess unbound water has led to flooding of the ion conductive channels and low hydroxide ion conductivity. The optimal anion conductivity was found with about 6.7 unbound and 11.9 bound water molecules per ion pair. Excellent hydroxide conductivity (> 120 mS/cm at 80 °C) was obtained at an ion-exchange capacity of 1.88 meq/g. The results show that hydroxide mobility is aided by phase segregation within the copolymer. The ion conducting polymer was stable in 1M NaOH solution at 80 °C, showing essentially no loss in ion conductivity in 1200 h. Thermogravimetric analysis showed that the membrane backbone was stable up to 400 °C, consistent with previous polynorbornene-based materials. The peak power density of a H 2 /O 2 , hydroxide conducting fuel cell containing one of these membranes was 542.57 mW/cm 2 at 0.43 V and current density of 1.26 A/cm2 at 60 °C.

08 HYDROGEN↗

Ultrafiltration membranes from polymerization of self-assembled Pluronic block copolymer mesophases

Industrially, ultrafiltration (UF) membranes are produced through non-solvent induced phase separation (NIPS), but due to environmental hazards inherent to the NIPS process as well as the low surface porosity and fouling resistance of membranes produced via this method, an alternative route to UF membranes is desirable. Here, this work presents the self-assembly of Pluronic block copolymers in the presence of water and a monomeric phase as a new technique for the preparation of UF membranes without the need for organic solvent or post-modification. Different compositions of block copolymer, water, and monomer were polymerized to obtain both hexagonal and lamellar mesostructures, as indicated by small angle X-ray scattering (SAXS) and cross-polarized light microscopy. As-synthesized membranes were found to have pore sizes in the range of 3–4 nm with a molecular weight cutoff of 1500 g/mol and displayed both excellent fouling resistance and high permeance of water, vastly outperforming a conventional NIPS UF membrane. Additionally, in contrast to NIPS, the proposed method provides flexibility in terms of both the final membrane chemistry and pore size. As such, it is a versatile approach that can be easily tailored to produce membranes for a wide range of applications including wastewater treatment and food processing.

36 MATERIALS SCIENCE↗

A rationally designed polysulfide-trapping interface on the polymeric separator for high-energy Li–S batteries

A coating layer consisting of a layer of graphene oxide (GO) inserted in between two layers of multi-walled carbon nanotubes (MWCNT) forms a multifunctional polysulfide-trapping triple-interface on the polymeric separator for lithium–sulfur (Li–S) batteries. The top and bottom highly conductive MWCNT interfaces are able to physically inhibit polysulfide diffusion and effectively reutilize the trapped active material during cycling. The inserted ultrathin GO layer with negatively charged carboxyl groups, on the other hand, electrostatically repels the migrating polysulfide anions. The stacked GO sheets also extensively prolong the migration routes of the polysulfides. Additionally, the “buffer zones” interspersed within the triple-interface accommodate the migrating polysulfides. Thus, the sandwiched separators enable Li–S cells with a high-sulfur-loading (10 mg cm -2 ), high areal capacity (10.9 mA h cm -2 ), and stable cycling ability even though the coating layer is ultra-thin (~17 μm) and light-weight (~0.23 mg cm -2 ).

25 ENERGY STORAGE↗

A novel polymeric lithicone coating for superior lithium metal anodes

Lithium metal (Li) is commonly regarded as the “holy grail” of rechargeable batteries and can serve as anodes for constituting various high-energy lithium metal batteries (LMBs). However, it suffers from two notorious issues: (1) continuous formation of inhomogeneous solid electrolyte interphase and (2) Li dendritic growth. Here, in this study, we developed a novel polymeric lithicone via a new molecular layer deposition (MLD) process, using lithium tert-butoxide (LTB) and hydroquinone (HQ) as precursors. We revealed that such an MLD process enabled the resultant LiHQ to grow linearly in a highly controllable and cyclic mode at a growth rate of 4 Å cycle −1 . Furthermore, its low process deposition temperature of 150 °C made it possible to practice high-quality coatings over Li anodes directly. We demonstrated that, very compellingly, this LiHQ coating could protect Li anodes from corrosion and dendritic growth. As a consequence, this LiHQ coating has enabled Li||Li symmetric cells an extremely long cyclability up to 8000 Li-plating/stripping cycles without failure. More excitingly, we demonstrated that, coupled with LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) cathodes, the LiHQ-modified Li anodes could help the resultant Li||NMC811 realize a much better capacity retention and much longer cyclability. Thus, this study represents a strategic route for developing commercializeable LMBs.

25 ENERGY STORAGE↗

Ring-opening metathesis polymerization of cobaltocenium derivative to prepare anion exchange membrane with high ionic conductivity

Abstract An efficient method to incorporate a cobaltocenium cation into polymers for anion exchange membranes is described. A cobaltocenium-containing norbornene derivative has been synthesized. It can be homopolymerized, or copolymerized with norbornene, by ring-opening metathesis polymerization (ROMP) with quantitative yields. The composition of the random copolymers can be precisely controlled by adjusting the feed ratio of the monomers. Additionally, the resulting polymers can be cast into thin robust membranes. The morphology of the membranes is characterized by humidity controlled SAXS and TEM, showing disordered interconnected cobaltocenium domains. The high ionic conductivity suggests that such membranes are good candidates for anion exchange membranes.

42 ENGINEERING↗

Organization of Lithium Cubane Clusters into Three-Dimensional Porous Frameworks by Self-Penetration and Self-Polymerization

Metal–organic frameworks based on lithium inherit the unique chemical and structural features of the metal ion itself. While the monomeric lithium node, usually 4-connected, is very desirable for designing zeolite-type networks, the resulting lithium MOF usually has limited stability, especially for 3-connected nets due to the solvent termination. The conventional design strategy based on lithium aryloxide clusters makes use of phenol-type ligands for cluster formation and a separate bifunctional ligand for cross-linking, which also leads to 4-connected nets. By integrating the roles of cluster-formation and framework-formation into a single ligand, 4-hydroxypyridine was previously shown to give a highly stable 8-connected framework. Still, its shortness and rigidity limit both the porosity and the type of framework topologies. Here, we demonstrate the new chemical and structural features of lithium cubane clusters with an elongated ligand, which results in two high-connected 3-D framework materials characterized by self-penetration and self-polymerization, respectively, unlike the commonly observed interpenetration. Such a method provides a feasible path to tune both stability and porosity in lithium-based MOFs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thin-Film Fracture Behavior for Diketopyrrolopyrrole Semiconducting Polymeric Films

Fracture energy, which quantifies a material’s resistance to the propagation of a pre-existing crack, is a key parameter for ensuring the mechanical reliability of stretchable organic electronic devices. However, most existing methods, such as a four-point bending fracture energy, utilized for measuring the fracture energy of semiconducting polymeric thin films are complicated by substrate effects, making it challenging to isolate the intrinsic behavior of the film from interfacial influences. In this study, we employed a pseudo free-standing pure shear method to systematically investigate the cohesive fracture energy of poly(diketopyrrolopyrrole-terthiophene) P(DPP-T)-based thin films to examine the effects of nanoconfinement, side chain length, degree of crystallinity, and strain rates. This method effectively eliminates substrate interference, enabling a direct assessment of the cohesive fracture energy of P(DPP-T) thin films. We found that thinner films and those with lower molecular weights exhibited significantly reduced fracture energies due to diminished chain entanglements. Additionally, films with shorter side chains displayed notably higher fracture energies, which were attributed to an increase in the degree of crystallinity. Finally, slower strain rates led to higher fracture energies, consistent with an enhanced stress relaxation. These insights offer practical guidelines for designing mechanically robust semiconducting polymers, contributing to the advancement of reliable, durable, flexible, and wearable electronic devices.

Zhang, Song [Univ. of Southern Mississippi, Hattie↗

Revealing the Charge Transport Mechanism in Polymerized Ionic Liquids: Insight from High Pressure Conductivity Studies

Polymerized ionic liquids (polyILs), composed mostly of organic ions covalently bonded to the polymer backbone and free counterions, are considered as an ideal electrolytes for various electrochemical devices, including fuel cells, supercapacitors and batteries. Despite large structural diversity of these systems, all of them reveal a universal but poorly understood feature - a charge transport faster than the segmental dynamics. Here, to address this issue, we have studied three novel polymer electrolyte membrane for fuel cells as well as four single-ion conductors including highly conductive siloxane-based polyIL. Our ambient and high pressure studies revealed fundamental differences in the conducting properties of the examined systems. Finally, we demonstrate that the proposed methodology is a powerful tool to identify the charge transport mechanism in polyILs in general and thereby contribute to unraveling the microscopic nature of the decoupling phenomenon in these materials.

36 MATERIALS SCIENCE↗

Stable Postfullerene Solar Cells via Direct C–H Arylation Polymerization. Morphology–Performance Relationships

The scope of the environmentally benign direct C–H arylation polymerization (DARP) process is validated and significantly extended in the synthesis of a high-performance benzodithiophene-based copolymer series, PBDT(Ar)-FTTE, with previously untested and systematically varied heteroaryl (Ar) substituents. Bulk-heterojunction (BHJ) polymer solar cells (PSCs) containing the high-performance nonfullerene acceptor (NFA) ITIC-Th and DARP-derived donors are fabricated and evaluated, yielding PCEs as high as 8%. The relationships between Ar-sensitive copolymer structure, BHJ morphology, and PSC performance are elucidated through in-depth characterization of structural order, phase separation, and charge transport using SCLC, AFM, GIWAXS, R-SoXS, and NEXAFS measurements, which conclusively demonstrate the important effects of Ar-tunable, dimensionally smaller, and well-blended copolymer domains for maximum PSC performance. Smaller BHJ copolymer domains having greater ITIC-Th miscibility definitively correlate with enhanced JSC, FF, and PCE metrics. Surprisingly regarding cell performance durability, while unencapsulated PBDTT-FTTE:ITIC-Th PSCs deliver the highest initial PCE, the unencapsulated PBDTTF-FTTE:ITIC-Th devices exhibit the optimum combination of high initial photovoltaic metrics and stability, retaining nearly 90% of the initial PCE after 51 days in ambient conditions and 83% of initial PCE after 180 min under simulated solar illumination. Importantly, for this PBDT(Ar)-FTTE:ITIC-Th series, PSC photovoltaic stability correlates with the presence of large pure BHJ domains, and moreover rivals or exceeds the stability of the analogous fullerene-based PSCs. Together, the results argue that solar cells prepared with the environmentally benign DARP process and NFAs are promising for both greener and more stable solar energy generation.

36 MATERIALS SCIENCE↗

Polymeric Microcapsules as Robust Mimics of Emulsion Liquid Membranes for Selective Ion Separations

Selective ion separations are increasingly needed to combat water scarcity, recover resources from wastewater, and enable the efficient recycling of electronics waste. Emulsion liquid membranes (ELMs) have received interest due to rapid kinetics, high selectivities, and low solvent requirements but are too unstable for industrial usage. Here, we demonstrate that polymeric microcapsules can serve as robust, solvent-free mimics of ELMs. As a proof of concept, we incorporated the copper-selective ligand Lix 84-I in the walls of microcapsules formed from a commercial polystyrene-b-polybutadiene-b-polystyrene triblock polymer. The microcapsules were formed from a double-emulsion template, resulting in particles typically 20–120 μm in diameter that encapsulated even smaller droplets of a dilute (≤0.5 M) H 2 SO 4 solution. Batch experiments demonstrated facilitated-transport behavior, with equilibrium reached in as little as 10 min for microcapsules with 1% ligand, and with ~15-fold selectivity for Cu 2+ over Ni 2+ . Furthermore, the microcapsules could be packed readily in columns for flow-through operation, thus enabling near-complete Cu 2+ removal in ~2 min under certain conditions, recovery of Cu 2+ by flowing through fresh dilute H 2 SO 4 , and reuse for at least 10 cycles. The approach in this work can serve as a template for using selective ligands to enable robust and simple flow-through processes for a variety of selective ion separations.

54 ENVIRONMENTAL SCIENCES↗

Gas Permeation and Separation Characteristics of Microporous TpHz COF Membranes Synthesized by Substrate-Assisted Interfacial Polymerization

Microporous two-dimensional covalent organic framework (2D COF) membranes offer promise for gas separation applications, but their gas transport mechanism remains unclear. In this study, a TpHz 2D COF membrane supported on a macroporous nylon substrate is prepared by substrate-assisted interfacial polymerization under mild conditions. The formation of a continuous and dense thin (~300 nm thick) TpHz layer is confirmed by scanning electron microscopy and Fourier transform infrared spectroscopy. Characterization by X-ray diffraction, grazing incidence wide-angle X-ray scattering, and N 2 porosimetry qualitatively reveals the microstructures of the supported TpHz membranes, i.e., they comprise partially oriented 2D COF lamellar crystallites with moderate crystallinity in an eclipsed (AA) stacking geometry, centering the effective membrane pore size distribution at ~1.1 nm. Further, single gas permeation data show that the transport of common molecular gases, including H 2 , He, CH 4 , N 2 , and CO 2 , through the synthesized TpHz membranes follows the Knudsen transport mechanism, where single gas permeance decreases with an increasing molecular weight and permeation temperature. Binary gas separation results show that in the equimolar CO 2 /N 2 mixture, the presence of the CO 2 surface flow slightly hinders the N 2 flow at room temperature due to the reduced membrane channel size by the adsorbed CO 2 gas layer on TpHz’s pore wall. In contrast, permeation of the equimolar CH 4 /N 2 binary mixture does not exhibit a discernible surface flow of both gases due to their much lower gas uptake on TpHz, and their transport mechanism follows Knudsen-like behavior.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tailoring Pore Architecture and Heteroatom Functionality of Polymeric Waste-Derived Nanoporous Carbon for CO 2 Capture Applications

This study proposes upcycling polymeric waste, i.e., waste floral foam, into high-performance nanoporous carbon that efficiently captures CO 2 . This paper presents strategies for improving the properties of nanoporous carbon, which aid in a superior CO 2 capture performance. Initially, pristine nanoporous carbon was produced from waste floral foam using various KOH impregnation ratios. The nanoporous carbon with a 1:2 (waste floral foam:KOH) ratio exhibiting optimal CO 2 capture capability was further advanced through single and dual atom doping. The doping of N and codoping of N,S atoms into the nanoporous carbon altered its textural and surface chemical properties, making them efficient for CO 2 capture. Comparative CO 2 capture studies of pristine nanoporous carbon (NC-x), N-doped nanoporous carbon (N-NC2), and N,S-codoped nanoporous carbon (N,S-NC2) demonstrate the superiority of N-doping. N-doped nanoporous carbon exhibited the largest ultramicroporosity (0.3100 cm3/g, 63.43%) and highest heteroatom content (34.94 atomic %), contributing to its enhanced CO 2 capture capability (4.54 mmol/g). Finally, implementing the “waste-to-depollution” approach, this research lays the groundwork for producing low-cost, environmentally friendly nanoporous carbon with remarkable CO 2 capture attributes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A poly(acrylonitrile)-functionalized porous aromatic framework synthesized by atom-transfer radical polymerization for the extraction of uranium from seawater

In order to ensure a sustainable reserve of fuel for nuclear power generation, tremendous research efforts have been devoted to developing advanced sorbent materials for extracting uranium from seawater. In this work, a porous aromatic framework (PAF) was surface-functionalized with poly(acrylonitrile) through atom-transfer radical polymerization (ATRP). Batches of this adsorbent were conditioned with potassium hydroxide (KOH) at room temperature or 80 °C prior to contact with a uranium-spiked seawater simulant, with minimal differences in uptake observed as a function of conditioning temperature. A maximum capacity of 4.81 g-U/kg-ads was obtained following 42 days contact with uranium-spiked filtered environmental seawater, which demonstrates a comparable adsorption rate. A kinetic investigation revealed extremely rapid uranyl uptake, with more than 80% saturation reached within 14 days. Furthermore, relying on the semiordered structure of the PAF adsorbent, density functional theory (DFT) calculations reveal cooperative interactions between multiple adsorbent groups yield a strong driving force for uranium binding.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Role of Fast Dynamics in Conductivity of Polymerized Ionic Liquids

Polymerized ionic liquids (PolyILs) are promising candidates for a broad range of technologies. However, the relatively low conductivity of PolyILs at room temperature has strongly limited their applications. In this work, we provide new insights into the roles of various microscopic parameters controlling ion transport in these polymers, which are crucial for their rational design and practical applications. Using broadband dielectric spectroscopy and neutron and light scattering techniques, we found a clear connection between the activation energy for conductivity, fast dynamics, and high-frequency shear modulus in PolyILs at their glass transition temperature (T g ). In particular, our analysis reveals a correlation between conductivity and the amplitude of fast picosecond fluctuations at T g , suggesting the possible involvement of fast dynamics in lowering the energy barrier for ion conductivity. We also demonstrate that both the activation energy for ion transport and the amplitude of the fast fluctuations depend on the high-frequency shear moduli of PolyILs, thus identifying a practically important parameter for tuning conductivity. Finally, the parameters recognized in this work and their connection to the ionic conductivity of PolyILs set the stage for a deeper understanding of the mechanism of ion transport in PolyILs in the glassy state.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Adaptive Data-Driven Deep-Learning Surrogate Model for Frontal Polymerization in Dicyclopentadiene

Frontal polymerization (FP) is a self-sustaining curing process that enables rapid and energy-efficient manufacturing of thermoset polymers and composites. Computational methods conventionally used to simulate the FP process are time-consuming, and repeating simulations are required for sensitivity analysis, uncertainty quantification, or optimization of the manufacturing process. Here, in this work, we develop an adaptive surrogate deep-learning model for FP of dicyclopentadiene (DCPD), which predicts the evolution of temperature and degree of cure orders of magnitude faster than the finite-element method (FEM). The adaptive algorithm provides a strategy to select training samples efficiently and save computational costs by reducing the redundancy of FEM-based training samples. The adaptive algorithm calculates the residual error of the FP governing equations using automatic differentiation of the deep neural network. A probability density function expressed in terms of the residual error is used to select training samples from the Sobol sequence space. The temperature and degree of cure evolution of each training sample are obtained by a 2D FEM simulation. The adaptive method is more efficient and has a better prediction accuracy than the random sampling method. With the well-trained surrogate neural network, the FP characteristics (front speed, shape, and temperature) can be extracted quickly from the predicted temperature and degree-of-cure fields.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mechanism of conductivity relaxation in liquid and polymeric electrolytes: Direct link between conductivity and diffusivity

Combining broadband impedance spectroscopy, differential scanning calorimetry, and nuclear magnetic resonance we analyzed charge and mass transport in two polymerized ionic liquids and one of their monomeric precursors. In order to establish a general procedure for extracting single-particle diffusivity from their conductivity spectra, we critically assessed several approaches previously employed to describe the onset of diffusive charge dynamics and of the electrode polarization in ion conducting materials. Based on the analysis of the permittivity spectra, we demonstrate that the conductivity relaxation process provides information on ion diffusion and the magnitude of cross-correlation effects between ionic motions. A new approach is introduced which is able to estimate ionic diffusivities from the characteristic times of conductivity relaxation and ion concentration without any adjustable parameters. Furthermore, this opens the venue for a deeper understanding of charge transport in concentrated and diluted electrolyte solutions.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Influence of Chain Rigidity and Dielectric Constant on the Glass Transition Temperature in Polymerized Ionic Liquids

Polymerized ionic liquids (PolyILs) are promising candidates for a wide range of technological applications due to their single ion conductivity and good mechanical properties. Tuning the glass transition temperature (T g ) in these materials constitutes a major strategy to improve room temperature conductivity while controlling their mechanical properties. In this paper, we show experimental and simulation results demonstrating that in these materials T g does not follow a universal scaling behavior with the volume of the structural units V m (including monomer and counterion). Instead, T g is significantly influenced by the chain flexibility and polymer dielectric constant. We propose a simplified empirical model that includes the electrostatic interactions and chain flexibility to describe T g in PolyILs. Finally, our model enables design of new functional PolyILs with the desired T g .

36 MATERIALS SCIENCE↗