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At least 739 records · Page 41

Constructing a multi-functional polymer network for ultra-stable and safe Li-metal batteries

We report the practical application of lithium (Li) metal electrodes is impeded by Li dendrite growth and unstable solid electrolyte interphase (SEI). Herein, a multi-grafting polymer network, poly(dimethyl siloxane)-g-[poly(poly(ethylene glycol) methyl ether methacrylate)-r-sodium poly(p-styrene sulfonate)] (PPS), is chemically synthesized from reversible addition-fragmentation chain transfer (RAFT) polymerization. With integrated stretchability, ionic conductivity, and mechanical robustness, it serves a dual role to stabilize the Li electrode. As artificial SEI layer, the PPS enables superior electrochemical performance in half cells, symmetric cells, and full cells (PPS@Li/LiFePO 4 , capacity retention of >70% after 600 cycles). Utilized as solid polymer electrolyte (SPE), the all-solid-state Li/SPE/LiFePO 4 full cell delivers excellent cycling performance with an unprecedented capacity retention of 90% over 1,700 cycles at 0.5 C and 81% over 1,000 cycles at 1.0 C. With high-voltage LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) as cathode, the Li/SPE/NMC811 cell exhibits an initial discharge capacity of 162.2 mAh g -1 with a capacity retention of 72% after 200 cycles. The assembled solid-state Li/SPE/LiFePO4 pouch cell with SPE exhibits stable cycling performance over 200 cycles with a capacity retention of 75% and still operates well even after curling, folding, and cutting, demonstrating great potential for achieving ultra-safe and high energy density batteries.

25 ENERGY STORAGE↗

Low-Velocity Impact Performances of Healed Polymer Fiber Reinforced Plastics

Extending the lifecycle of traditional carbon or glass fiber-reinforced plastics is a complicated problem. The lack of sustainability limits the applications of the traditional composite materials in the vehicle industries where recycling and repurposing are critical issues. Alternatives for the low-stressed structural components are polymer fiber-reinforced plastics (PFRPs). In PFRPs, both the fibers and matrix are composed of thermoplastic polymers (e.g. polypropylene or polyethylene). They are lightweight, easy to manufacture, and cost-effective. Additionally, recycling and repurposing thermoplastic polymers are well understood. Therefore, the PFRPs have strong advantages compared to the traditional fiber-reinforced composites in low-stressed structural applications. In this study, we investigated the low-velocity impact (LVI) performances of the PFRPs and compared them with carbon fiber-reinforced plastics (CFRPs). A semi-spherical impactor was dropped to flat, square panels, and the absorbed impact energy was measured. The damage mechanisms were examined using a Xray µCT scan. The PFRPs outperformed the CFRPs in terms of perforation energy normalized by plate thickness and density. After the perforation, we healed the fractured plates by leveraging the recyclability of the thermoplastic polymers. The healing process of the panels was identical to the initial panel manufacturing process. No additional materials were added during the healing process. The healed PFRP panels were impacted again and substantially recovered energy absorption capability. We also conducted the repeated-impact test with several different impact energies. Unlike the CFRPs where the impact peak load decreased as the impacts repeated, the PFRPs showed an increasing trend. Such a unique mechanism was due to the strain-hardening behavior of the polymer fibers and matrix. As a result, the repeated-impact life of the PFRPs was significantly enhanced. These results are particularly interesting in the automotive or aerospace industries where repeated LVI is frequently observed.

Ko, Seunghyun↗

A Bis(arenesulfonyl) Peroxide, an Ambient-Stable Oxidant, Is a Strong p-Dopant for Organic Semiconductors

Strong p-dopants are required to dope high-ionization energy organic semiconductors for a variety of potential applications, but strong, simple one-electron oxidants are typically sensitive to reduction by atmospheric moisture and thus challenging to store or handle. Here we show that bis(3,5-bis(trifluoromethyl)benzenesulfonyl) peroxide─a dimer formed by two highly oxidizing radicals─can function as a water-stable yet powerful oxidant, cleanly reacting with some organic semiconductors to form two radical cations and two 3,5-bis-(trifluoromethyl)benzenesulfonate anions, although in other cases sulfonylation reactions can also occur. Notably, this peroxide is capable of p-doping the high-ionization energy polymer poly[(9,9-dioctylfluorene-2,7-diyl)- alt -(benzo[2,1,3]thiadiazol-4,7-diyl)] (F8BT) to afford electrical conductivities of up to 0.03 S cm –1 , while its use with electron-rich poly(3,4-dialkoxythiophene-2,5-diyl) derivatives can afford values up to 100 S cm –1 . Quantum-chemical calculations reveal the peroxide oxidant behaves in a fashion mirroring that of relatively oxygen-stable, but highly reducing, n-dopants that have been developed based on dimers of organic radicals or organometallic sandwich compounds.

doping↗

Methods for manufacturing electrochemical sensors, and related electrochemical sensors

Methods for manufacturing an electrochemical sensor include forming at least one electrode by printing at least one conductive ink on a surface of at least one substrate. The conductive ink may comprise, e.g., a platinum-group metal, another transition-group metal with a high-temperature melting point, a conductive ceramic material, glass-like carbon, or a combination thereof. The electrochemical sensor may be free of another material over the at least one electrode. An electrochemical sensor, formed according to such methods, may be configured for use in harsh environments (e.g., a molten salt environment). Electrodes of the electrochemical sensor comprise conductive material formed from a printed, conductive ink. In some embodiments, at least a portion of the electrochemical sensor is free of silver, gold, copper, silicon, and polymer materials, such portion being that which is to be exposed to the harsh environment during use of the electrochemical sensor.

Shaltry, Michael R.↗

Mechanically Reinforced Pseudosolid Polyelectrolyte Membranes via Layer-by-Layer Assembly for High-Performing Lithium-Metal Batteries

Ionogels are emerging as high-potential pseudosolid electrolytes for lithium-metal batteries (LMBs), leveraging their intrinsic high ionic conductivity from entrapped ionic liquid (IL) electrolytes. However, their practical application is hindered by poor mechanical strength stemming from the confinement of ILs within a polymer matrix. To address this challenge, the formation of conformal polyion coatings with functional groups is reported to be relevant to LMBs’ application on ionogels, utilizing a layer-by-layer (LbL) assembly strategy. Here, this approach significantly enhances the mechanical strength (Young's modulus and tensile strength) and electrochemical performance of ionogels, owing to the tailored interface modifications introduced by functional groups’ specific conformal polyion coatings. The core of this methodology leverages the inherent ionic structure of ionogels to enable facile interface modification through Coulombic interactions between polyanions and polycations. These conformally coated interface functionalized membranes show improved electrochemical performance when integrated with cathode materials such as LiFePO 4 (LFP) and LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) in an LMB configuration, underscoring their potential for robust, high-conductivity, pseudosolid membranes for LMB applications. These innovative pseudosolid membranes offer improved mechanical and electrochemical properties, leading to higher battery efficiency and safety, making them promising candidates for next-generation LMB technology.

25 ENERGY STORAGE↗

Thermal and Electrical Properties of Isocyanate Derived Organic Aerogels for Cryogenic Insulation Applications

The use and storage of cryogens such as liquefied nitrogen, helium, hydrogen among others requires reliable and efficient thermal insulation systems. Passive insulation from high performance materials that are well-known for their inherent low thermal conductivity would reduce the overall costs involved in design, manufacture and maintenance of such systems. One such class of materials are referred to as aerogels. These materials are known for their low density, high mesoporosity, high surface areas, low thermal conductivity and high acoustic impedance. Aerogels were invented by S.S. Kistler in 1931 and the most common type are those made of silica. However, the inherent fragility of silica aerogels makes them hard to mass produce, and therefore applications have been limited. A major breakthrough was introduced by our team almost 20 years ago with the invention of polymer crosslinked silica aerogels. Those materials shifted attention to all-polymer aerogels that have overcome all fragility issues associated with their inorganic counterparts. This study focuses on such polymeric aerogels that can be mass produced as large monoliths while maintaining the low thermal conductivity of traditional silica aerogels over a wide temperature range. Manufacturing flexibility of polymeric aerogels allows fabrication of blocks and sheets that can be applied in various configurations to insulate cryogenic and superconducting devices. The thermal conductivity with 80 K and room temperature boundary are reported as well as other properties (electrical), that need to be considered when designing devices for cryogenic applications.

Churu, Gitogo↗

Validation of Advanced Photovoltaic Module Materials and Processes by Combined-Accelerated Stress Testing (C-AST)

Tessolar module technology was developed to allow the incorporation of 5 incremental module material innovations. Combined, these innovations may improve the efficiency and durability of the standard silicon cell module. The innovations evaluated are: electrically conductive adhesive (ECA) replacing soldering of tabbing ribbons, light-capturing ribbon (LCR), silicone encapsulant, 2 mm front glass with backsheet, and a polymer-composite module frame. Tessolar-constructed individually encapsulated cells incorporating the material innovations are used to assemble 60-cell modules. 2 x 2 cell mini-modules of the same materials were produced for combined-accelerated stress testing (C-AST). C-AST results demonstrate that the 2 x 2 cell mini-module of Tessolar construction out-performed mini-modules using both ECA with EVA and standard solder with EVA constructions in power production over 108 cycles of testing.

14 SOLAR ENERGY↗

Effect of Crystallinity on Polymer Chain Compression in Polyethylene Dynamically Loaded with In-Situ X-Ray Diffraction

Abstract Polyethylene (PE) is a polymer widely used in commercial applications, where the properties of PE can be altered based on the molecular conformation. In this study, shock compression experiments with in-situ x-ray diffraction were conducted on two conformations of PE– low density polyethylene (LDPE) and ultra-high molecular weight polyethylene (UHMWPE). Encouragingly, X-ray diffraction patterns were easily observed in LDPE, which is only 25% crystalline. In agreement with a previous study on HDPE, LDPE exhibited a phase transition at 7.7 GPa. Lower pressure experiments on UHMWPE and LDPE exhibited polymer chain compression, but no occurrence of a phase transition.

36 MATERIALS SCIENCE↗

Tracking Spatiotemporal Electric Potential in Batteries Using High-Resolution Operando X‑ray Transmission Imaging

The formation of significant concentration gradients across electrolytes in batteries affects the rate at which electrochemical reactions occur. In this work, we use high-resolution operando X-ray transmission imaging to capture spatiotemporal salt concentration profiles c(x,t) in a symmetric cell comprising a polymer electrolyte sandwiched between two lithium–indium alloy electrodes during a constant-current experiment followed by open-circuit relaxation. The decay of open-circuit potential is related to the concentration dependence of the potential across concentration cells, U. We show how operando c(x,t) data can be used to calculate the spatiotemporal electric potential “inside” the polarized electrolyte. We track the spatial- and time-dependent cell potential during the constant-current step and distinguish its two contributions: a concentration overpotential governed by U. and an ohmic contribution governed by ionic conductivity. Over most of the time window, the concentration overpotential dominates. At steady state, it is a factor of 7 larger than the ohmic contribution. Such findings indicate that efforts to design new polymer electrolytes should focus on minimizing concentration gradients.

Electrical conductivity↗

Bipolar Membranes Electrodialysis for Water Purification and Resource Recovery

Reverse osmosis concentrate (ROC) from inland brackish water desalination and wastewater recycling presents moderate salinity, posing significant challenges for treatment and disposal. Existing treatment technologies predominantly rely on energy-intensive thermal methods, large-area evaporation strategies, or deep-well disposal, which often result in the loss of water value. Electrified membrane brine treatment offers a promising alternative by utilizing renewable energy sources, enabling complete water recycling. This work proposes the development of next-generation bipolar membrane electrodialysis (BMED) systems capable of desalinating brine while simultaneously recovering valuable resources. However, several critical challenges remain in the areas of membrane engineering for BMED. These include: 1) decreased current efficiency during desalination due to the low conductivity of feed chambers, 2) fouling and scaling from multivalent ions and contaminants in the feed, and 3) the retention and carryover of ROC contaminants, including PFAS compounds. Our research focuses on the development of novel anion exchange membranes (AEMs) and cation exchange membranes (CEMs) based on synthesized multiblock copolymers. We investigate the effects of block length, ion exchange capacity (IEC), and polymer backbone structure on cation and anion transport (e.g., Na+, Cl-, OH-, H+) for both our synthesized membranes and commercial membranes. Fundamental properties of these membranes, such as water uptake, IEC, and ionic conductivity, are also evaluated to optimize performance for BMED applications.

08 HYDROGEN↗

Increased Static Charge–Induced Threshold Voltage Shifts and Memristor Activity in Pentacene OFETs Comprising Polystyrene–Based Gate Dielectrics Containing Electroactive Small Molecule Crystallites

Top-contact bottom-gate pentacene OFETs are fabricated with single layer dielectrics comprised of either polystyrene (PS), poly(4-methylstyrene) (P4MS), or poly(4-tert-butylstyrene) (P4TBS). The polystyrenes are blended with varying concentrations of two different small molecules, dibenzotetrathiafulvalene (DBTTF) and 2,8-difluoro-5,11-bis(triethylsilylethynyl)anthradithiophene (diF-TES-ADT), to form small, separated crystallites contained throughout the polymer dielectric layer. The OFET characteristics of these devices are investigated and their threshold voltage shifts are measured after –70 V static charging for 5 min. Two-terminal measurements are conducted using multiple different gate biases in the range of –50 to +50 V to investigate memristor behavior in the devices. OFETs containing DBTTF exhibited ΔVth increases as large as 330% relative to control OFETs containing no DBTTF, while OFETs containing at least 7.5 wt.% DBTTF exhibited memristor activity, with currents ranging from 20 nA to 44 µA depending on the applied bias. Furthermore, this work demonstrates that including small, separated crystallites in polymer dielectrics enhances their charge storage ability and can be promising for creating nonbinary memory devices for data processing. Additionally, the observed memristor activity indicates the OFETs in this work can be used in development of neuromorphic systems that aim to mimic the synaptic behavior of the human nervous system.

25 ENERGY STORAGE↗

Investigation of SiO x anode fading mechanism with limited capacity cycling

Silicon suboxide (SiO x ) is one of the promising anode materials for the next-generation lithium-ion batteries. However, SiO x has a severe capacity fading problem during cycling. It is thus desired to investigate the detailed fading mechanisms of SiO x anode materials. In this study, limited capacity cycling was employed to examine the electrochemical behaviors of the SiO x anode, and the lithiation/delithiation cycling was limited within a range of 10% theoretical capacity. This strategy minimizes the volume variation of SiO x materials upon charging/discharging, which helps to reveal their decay factors other than volume fluctuation. It is demonstrated that the instability of the SiO x surface during cycling was likely a parallel factor of active material fading, which seems to cause unfavored electrode interface rearrangements with lowered electric conductivity.

electric vehicles↗

Autonomous alignment and healing in multilayer soft electronics using immiscible dynamic polymers

Self-healing soft electronic and robotic devices can, like human skin, recover autonomously from damage. While current devices use a single type of dynamic polymer for all functional layers to ensure strong interlayer adhesion, this approach requires manual layer alignment. In this study, we used two dynamic polymers, which have immiscible backbones but identical dynamic bonds, to maintain interlayer adhesion while enabling autonomous realignment during healing. These dynamic polymers exhibit a weakly interpenetrating and adhesive interface, whose width is tunable. When multilayered polymer films are misaligned after damage, these structures autonomously realign during healing to minimize interfacial free energy. Finally, we fabricated devices with conductive, dielectric, and magnetic particles that functionally heal after damage, enabling thin-film pressure sensors, magnetically assembled soft robots, and underwater circuit assembly.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Three-dimensional rechargeable battery with solid-state electrolyte

A scaffold of an electrolyte is fabricated in polymer material using 3D printing techniques. A thin layer of solid electrolyte is deposited on the scaffold followed by burning off the polymer. This leaves behind a 3D foam-like solid electrolyte with two distinct non-overlapping volumes. Lithium followed by a conductive layer (for anode) is then deposited through one volume on the first surface whereas a porous or non-porous conductive layer is deposited on the opposite surface through the second volume. The non-porous conductive layer on the second surface is made porous by a selective timed etch.

Saha, Sourabh K.↗

Poly(norbornene) anion conductive membranes: homopolymer, block copolymer and random copolymer properties and performance

It has previously been shown that phase-separated block copolymers with non-ion conducting (hydrophobic) blocks and ion conducting (hydrophilic) blocks can form efficient ion conducting channels with high ionic mobility and conductivity. Block copolymers can provide a means for phase segregation and ion channel formation while homopolymers and random copolymers have been shown to have lower ion mobility. In this study, the properties of poly(norbornene) based anion exchange membranes (AEMs) comprising homopolymers, block copolymers, and random copolymers with high ion-exchange capacity (IEC) (3.48–4.55 meq. g -1 ) have been investigated and compared. The polymers were cross-linked with N,N,N',N'-tetramethyl-1,6-hexanediamine before casting the membranes to avoid excessive water swelling due to high water uptake. It was shown that high ionic conductivity can be achieved in both random copolymers and homopolymers even in the absence of microphase-separated structures. For example, the conductivity of a random copolymer was 194 mS cm -1 at 80 °C, which was comparable to the block copolymer, 201 mS cm -1 at 80 °C. The H 2 /O 2 fuel cell performance of random copolymer composite membranes showed a peak power density of 3.05 W cm -2 and peak current density of 7.85 A cm -2 at 80 °C compared to block copolymer membranes (peak power density of 3.21 W cm -2 and peak current density of 8.27 A cm -2 at 80 °C). It is more critical that high water transport be achieved in AEMs than achieving a phase-segregated morphology. Finally, the homopolymer, block copolymer, and random copolymer membranes showed <1.35% degradation after aging in 1 M NaOH at 80 °C for 1000 h.

08 HYDROGEN↗

Fabrication of Piezoelectric Polymer and Metal–Organic Framework Composite Thin Films Using Solution Shearing

Polymer-metal–organic framework (polymer-MOF) composites have garnered significant interest as polymers can enhance the processability and industrial applicability of MOFs. Thin films of these composites are particularly attractive for applications in sensing, separations, and flexible electronics. Solution shearing, a meniscus-guided coating technique, has emerged as a scalable process for fabricating thin films of MOFs, and can produce large-area films within minutes. In this study, we utilized solution shearing to fabricate composite thin films of a MOF UiO-66 and a piezoelectric polymer poly(vinylidene fluoride-trifluoroethylene) (P(VDF-TrFE)), investigating how polymer concentration during MOF synthesis and composite formation influences thin film properties, including crystallinity, surface coverage, and piezoelectric performance. Additionally, solid-state NMR spectroscopy was utilized to probe the interactions between P(VDF-TrFE) and UiO-66 in the composite. Evidence from solid-state NMR indicated polymer-MOF interactions, suggesting that the polymer strands are in close proximity to the UiO-66 pores, supporting a mixed surface coating and pore infiltration model. Furthermore, incorporating P(VDF-TrFE) enhanced the film’s areal coverage from 70% to 100%. While the thermal conductivity remained essentially unchanged, the composite film showed an improved piezoelectric effect. The composite with 91 wt % P(VDF-TrFE) exhibited the highest output voltage of 9.1 V and a sensitivity of 0.26 V/N under applied pressure. This work demonstrates the potential of solution shearing as a scalable technique for fabricating polymer-MOF composite thin films.

P(VDF-TrFE)↗

Improving adhesive bonding of short carbon fiber thermoplastic composites to aluminum alloys with a hybrid laser-plasma surface modification strategy

This study investigates hybrid laser–plasma surface modification strategies for metal–CFRTP (carbon-fiber-reinforced thermoplastic polymer) dissimilar joints to improve their bonding performance, in contrast to existing literature that mostly focuses on either plasma or laser treatment alone. By conducting double cantilever beam (DCB) tests on adhesively-bonded AA5052 and CFRPA66 (carbon-fiber-reinforced polyamide 66) joints, as an example of metal–CFRTP joints, it was found that laser engraving on the metal surface combined with plasma treatment on the CFRTP surface significantly improved the specific fracture energy of the joint by 187% and 31% compared to as-received and plasma-treated-only joints, respectively. However, the hybrid treatment of laser engraving and plasma on the investigated CFRTP surface did not improve the bonding performance of the joints. The underlying mechanisms related to hybrid laser-plasma surface modification strategies were further investigated by examining the surface and cross-sectional morphologies after DCB testing using microscopy. Computational modeling was performed to elucidate the interaction between grooves on the metal substrate and the CFRTP–adhesive interfacial bonding in metal–CFRTP joints. This study provides new insights into developing surface modification methods for achieving strong metal–CFRTP adhesive joints, aimed at lightweighting structural components in automotive, aerospace, and other applications.

Adhesive bonding↗