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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 37 records · Page 2

Rational design of mechanically robust Ni-rich cathode materials via concentration gradient strategy

Mechanical integrity issues such as particle cracking are considered one of the leading causes of structural deterioration and limited long-term cycle stability for Ni-rich cathode materials of Li-ion batteries. Indeed, the detrimental effects generated from the crack formation are not yet entirely addressed. Here, applying physicochemical and electrochemical ex situ and in situ characterizations, the effect of Co and Mn on the mechanical properties of the Ni-rich material are thoroughly investigated. As a result, we successfully mitigate the particle cracking issue in Ni-rich cathodes via rational concentration gradient design without sacrificing the electrode capacity. Our result reveals that the Co-enriched surface design in Ni-rich particles benefits from its low stiffness, which can effectively suppress the formation of particle cracking. Meanwhile, the Mn-enriched core limits internal expansion and improve structural integrity. The concentration gradient design also promotes morphological stability and cycling performances in Li metal coin cell configuration.

36 MATERIALS SCIENCE↗

Reticular chemistry for the rational design of mechanically robust mesoporous merged-net metal-organic frameworks

Access to metal-organic frameworks (MOFs) with enhanced mechanical stability is key to their successful deployment in practical applications. However, the high porosity of the material often affects mechanical stability. In this article, to achieve highly porous MOFs with enhanced mechanical stability, we explored the merged-net approach where two relatively fragile frameworks were merged into a robust MOF structure. We demonstrate the effectiveness of this approach by computationally evaluating mechanical properties of sph-MOFs with varying lengths of linkers. Prominently, we pinpoint the significance of triangular rigidity on the robustness of large-pore MOFs and, subsequently, designed and synthesized a rare earth (RE)-based RE-sph-MOF-5 by the reticulation of hexanuclear RE clusters, tritopic linkers, and unprecedentedly large planar hexatopic linkers containing 19 phenyl rings. The mechanical properties of sph-MOFs were characterized and quantified using amplitude-frequency modulation (AM-FM) bimodal atomic force microscopy (AFM) analyses. Markedly, the mesoporous RE-sph-MOF-5 expresses high mechanical stability despite its large mesoporous cavities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Carboxylating Elastomer via Thiol‐Ene Click Reaction to Improve Miscibility with Conjugated Polymers for Mechanically Robust Organic Solar Cells with Efficiency of 19%

Abstract Incorporating flexible insulating polymers is a straightforward strategy to enhance the mechanical properties of rigid conjugated polymers, enabling their use in flexible electronic devices. However, maintaining electronic characteristics simultaneously is challenging due to the poor miscibility between insulating polymers and conjugated polymers. This study introduces the carboxylation of insulating polymers as an effective strategy to enhance miscibility with conjugated polymers via surface energy modulation and hydrogen bonding. The carboxylated elastomer, synthesized via a thiol‐ene click reaction, closely matches the surface energy of the conjugated polymer. This significantly improves the mechanical properties, achieving a high crack‐onset strain of 21.48%, surpassing that (5.93%) of the unmodified elastomer:conjugated polymer blend. Upon incorporating the carboxylated elastomer into PM6:L8‐BO‐based organic solar cells, an impressive power conversion efficiency of 19.04% is attained, which top‐performs among insulating polymer‐incorporated devices and outperforms devices with unmodified elastomer or neat PM6:L8‐BO. The superior efficiency is attributed to the optimized microstructures and enhanced crystallinity for efficient and balanced charge transport, and suppressed charge recombination. Furthermore, flexible devices with 5% carboxylated elastomer exhibit superior mechanical stability, retaining ≈88.9% of the initial efficiency after 40 000 bending cycles at a 1 mm radius, surpassing ≈83.5% for devices with 5% unmodified elastomer.

Chemistry↗

Porous but Mechanically Robust All-Inorganic Antireflective Coatings Synthesized using Polymers of Intrinsic Microporosity

Herein, we introduce polymer of intrinsic microporosity 1 (PIM-1) to design single-layer and multilayered all-inorganic antireflective coatings (ARCs) with excellent mechanical properties. Using PIM-1 as a template in sequential infiltration synthesis (SIS), we can fabricate highly uniform, mechanically stable conformal coatings of AlO x with porosities of ~50% and a refractive index of 1.41 compared to 1.76 for nonporous AlO x that is perfectly suited for substrates commonly used in high-end optical systems or touch screens (e.g., sapphire, conductive glass, bendable glass, etc.). We show that such films can be used as a single-layer ARC capable of reduction of the Fresnel reflections of sapphire to as low as 0.1% at 500 nm being deposited only on one side of the substrate. We also demonstrate that deposition of the second layer with higher porosity using block copolymers enables the design of graded-index double-layered coatings. AlO x structures with just two layers and a total thickness of less than 200 nm are capable of reduction of Fresnel reflections under normal illumination to below 0.5% in a broad spectral range with 0.1% reflection at 700 nm. Additionally, and most importantly, we show that highly porous single-layer and graded-index double-layered ARCs are characterized by high hardness and scratch resistivity. The hardness and the maximum reached load were 7.5 GPa and 13 mN with a scratch depth of about 130 nm, respectively, that is very promising for the structures consisting of two porous AlO x layers with 50% and 85% porosities, correspondingly. Such mechanical properties of coatings can also allow their application as protective layers for other optical coatings.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mechanically robust high magnetic-performance Sm-Co sintered magnets through microstructure engineering

Samarium-cobalt (Sm-Co) sintered magnets have high magnetic energy densities, great resistance to demagnetization and corrosion, and excellent thermal stability in a wide temperature range (–50–550 °C). However, the utilization of these magnets is restricted by their brittleness. Based on micromechanical and the Zener pinning model, Sm-Co sintered magnets with improved mechanical properties have been designed and fabricated via microstructure engineering. A small amount of fine Sm 2 O 3 particulates (0–3 wt%) has been incorporated into Sm 2 (CoFeCuZr) 17 sintered magnets to refine the grain size by up to approximately 50% (from 45 to 22 µm) and narrow the grain size distribution. Doping with 3 wt% Sm 2 O 3 increased the flexural strength by 62% while maintaining magnetic performance. Both grain-refined unimodal microstructure and heterogeneous laminated coarse/fine grain microstructure were formed by strategically designed assemblies of Sm 2 O 3 -added Sm-Co powder feedstock mixtures. The technology is compatible with existing magnet manufacturing processes. Numerical micromechanics simulation indicates that the fracture is dominated by intragranular mode. The mechanical strength is mainly enhanced by the additive-induced grain refinement, while the small amount of Sm 2 O 3 addition has a small direct positive contribution. Finally, these magnets will be more cost-effective, efficient, and robust for various functional applications.

36 MATERIALS SCIENCE↗

Mechanically Robust Bismuth-Embedded Carbon Microspheres for Ultrafast Charging and Ultrastable Sodium-Ion Batteries

Advancements in the development of fast-charging and long-lasting microstructured alloying anodes with high volumetric capacities are essential for enhancing the operational efficiency of sodium-ion batteries (SIBs). These anodes, however, face challenges such as declined cyclability and rate capability, primarily due to mechanical degradation reduced by significant volumetric changes (over 252%) and slow kinetics of sodium-ion storage. Herein, we introduce a novel anode design featuring densely packed bismuth (Bi) embedded within highly conductive carbon microspheres to overcome the aforementioned challenges. Remarkably, the high loading Bi anode within carbon microspheres with a high tap density of 2.59 g cm -3 possesses significant mechanical strength exceeding 590 MPa and limits volume swelling of only 10.9% post-sodiation. This anode demonstrates a high volumetric capacity (908.3 mAh cm -3 ), ultrafast chargeability (200 A g -1 , full charge/discharge in just 5.5 s), and outstanding cyclability over 12,000 cycles and maintains exceptional cycling stability even at -30 °C. The full cell paired with a Na 3 V 2 (PO 4 ) 3 cathode retains over 80% capacity after 600 cycles at 36 C, demonstrating a remarkable rate capability of 126 C (full charge/discharge in 28.6 s). Our comprehensive experimental evaluations and chemo-mechanical simulations shed light on the mechanisms underpinning the anode's superior performance. In conclusion, this development marks a significant advancement in the design of durable and fast-charging anodes for high-performance SIBs.

25 ENERGY STORAGE↗

Mechanically robust hydrophobized double network hydrogels and their fundamental salt transport properties

Abstract Water swollen polymer networks are attractive for applications ranging from tissue regeneration to water purification. For water purification, charged polymers provide excellent ion separation properties. However, many ion exchange membranes (IEMs) are brittle, necessitating the use of thick support materials that ultimately decrease throughput. To this end, novel double network hydrogels (DNHs) with variable water content are prepared and characterized in terms of mechanical and ion transport properties to evaluate their potential utility as tough membrane materials. The first network contains fixed anionic charges, while the other is comprised of a copolymer with varied ratios of hydrophobic ethyl acrylate (EA) and hydrophilic dimethyl acrylamide (DMA) repeat units. Characterization of freestanding DNH films reveals a reduction in water content from 88 to 53 wt% and a simultaneous increase in ultimate stress and strain by ~3.5× and ~4.5×, respectively, for 95%/5% EA/DMA, relative to 100% DMA. Fundamental salt transport properties relevant to water purification, including permeability, solubility, and diffusivity, are measured and systematically compared with conventional membrane materials to inform the development of DNHs for membrane applications. The ability to simultaneously reduce water content and increase mechanical integrity highlights the potential of DNHs as a synthetic platform for future membrane applications.

Allen, Marshall J.↗

Mechanically robust and reprocessable imine exchange networks from modular polyester pre-polymers

Covalent adaptable networks (CANs) containing reversible cross-links impart recyclability to thermoset materials without sacrificing their desirable properties (e.g. high tensile strength and solvent resistance). In addition to thermal recycling, the sustainability of these materials may be further improved by incorporating bio-sourced monomers or by enabling alternate end-of-life fates, such as biodegradation or recovery of starting materials. The alternating ring-opening copolymerisation of epoxides and cyclic anhydrides permits the modular synthesis of polyester pre-polymers that can then be cross-linked to form dynamic imine-linked networks. In this work, we report the synthesis and characterisation of five imine exchange polyester CANs with varied cross-linking densities and pre-polymer architectures. While the materials exhibit characteristic thermoset properties at service temperatures, differences in pre-polymer architecture produce distinct dynamic mechanical effects at elevated temperatures. The networks may be thermally reprocessed with full recovery of their tensile strengths and cross-linking densities, dissociated to pre-polymer, or hydrolytically degraded.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Efficient Construction of a C 60 Interlayer for Mechanically Robust, Dendrite-free, and Ultrastable Solid-State Batteries

Interfacial instability between solid electrolytes (SEs) and lithium metal remains a daunting challenge for solid-sate batteries. Here, a conformal C 60 interlayer is efficiently constructed on Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 (LAGP) SEs by physical vapor deposition, and an ideal interfacial contact is achieved via forming an ionically conducting matrix of LixC60 with lithium metal. The obtained Li x C 60 is beneficial to hinder the growth of lithium dendrites at interface and release the local stress during the lithiation and delithiation. As a result, the Li/LAGP-C 60 /Li symmetric cells demonstrate ultra-stable cycling performance for more than 4,500 h at a current density of 0.034 mA cm -2 . The Li/LAGP-C 60 /LiFePO 4 full cells deliver a reversible capacity of 152.4 mAh g -1 at room temperature, and the capacity retention rate is 85% after more than 100 cycles. This work provides a feasible and scalable strategy to improve the SEs/Li interface for high-performance solid-state batteries.

25 ENERGY STORAGE↗

Multifunctional entinostat enhances the mechanical robustness and efficiency of flexible perovskite solar cells and minimodules

Flexible perovskite solar cells (F-PSCs), prized for their nature of soft and high power-weight compatibility, have attracted intensive attention. However, inferior buried perovskite-substrate interfaces due to low interfacial adhesion between perovskites and substrates and large deformation of flexible substrates have greatly limited the performance of F-PSCs. Here, we add organic molecule Entinostat (ET) into hole extraction material Poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA) to enhance the adhesion at the perovskite/substrate interface using the interactions of ET with perovskites, PTAA and indium tin oxide (ITO) through its multiple function groups. Meanwhile, ET added into perovskites reduces the voids at the bottom perovskite film, due to its capability to tune the crystallization of perovskites by forming adduct with lead. Consequently, the inverted small area F-PSCs achieved an efficiency of 23.4%. The flexible perovskite minimodule with an area of 9 cm 2 achieved an aperture efficiency of ~19.0% certified by National Renewable Energy Laboratory. Furthermore, the optimized unencapsulated flexible minimodule retained 84% of the initial efficiency after 5000 bending cycles and retained 90% of the initial PCE (T90) after light soaking for >750 hours.

14 SOLAR ENERGY↗

Mechanically robust and superior conductive n-type polymer binders for high-performance micro-silicon anodes in lithium-ion batteries

Compared with nanostructured silicon (Si), the Si microparticle (SiMP) has more commercial prospects due to its low cost. However, SiMPs suffer from unavoidable fracture during electrochemical cycling owing to their significant volume change. Here we develop a series of novel n-type conductive polymer binders (CPBs) for SiMP anodes in lithium-ion batteries owing to their superior properties. Extraordinary electrochemical performance of cells with such unique binders could be achieved, which is because these designed polymers contain electron-withdrawing oxadiazole ring groups and easily ionizable sulfonate polar groups, exhibiting excellent ionic conductivity, outstanding wettability to the electrolyte, and improved electronic conductivity after doping. Moreover, the coexistence of rigid and flexible chains enables them to have exceptional strength and ductility. Besides, a unique electrochromic approach has been utilized to investigate the energy gap of the CPBs in n-doping states. The ionic and electronic conductivities of prepared CPBs in an eigenstate and n-doping state have been systematically studied by the electrochemical method, filling the current research gap in this field. Due to the high conductivity of b-POD, the capacity of SiMPs (4200 mA h g –1 ) can be almost entirely released during the first cycle of discharge, while the SiMP anodes prepared with the PAALi or CMC binder show a much lower initial capacity. Here, the high conductivity of b-POD also endows it with better cycling performance than non-conductive binders especially at high current densities, demonstrating its excellent fast-charging ability. More essentially, this work provides polymer binders without any intricate structural designs to obtain high-performance SiMP batteries, significantly enhancing their practical applications.

25 ENERGY STORAGE↗