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At least 289 records · Page 16

High-performance all-solid-state Li–S batteries enabled by an all-electrochem-active prelithiated Si anode

The development of all-solid-state Li–S batteries has been greatly impeded by dendrite growth and dendrite penetration, which are both related to the Li metal anode. As a compromised alternative, we report lithium silicide (Li x Si) as a dendrite-free and high-capacity anode with Li source. Here, the as-synthesized Li x Si is relatively soft, highly electronically conductive, and with a high Li diffusivity. These distinctive properties make Li x Si anode viable as an “all-electrochem-active” electrode (consisted of 100 wt.% Li x Si). Compared with the typical composite electrode, the all-electrochem-active electrode not merely maximizes the electrode-level energy density but also minimizes the electrolyte-related interfacial degradation. Li x Si symmetric cell demonstrates a reversible cycling at 4 mA cm –2 for over 320 h. Stress change and morphological evolution of the Li x Si electrode are investigated upon dealloying/alloying. When paired with a S cathode (active mass loading of 3 mg cm –2 ), Li x Si–S full cell shows a good cycling behavior over 500 cycles and rate performance (69% capacity retained at 1.2C) even at 25 °C.

25 ENERGY STORAGE↗

One‐Step Thermal Gradient‐ and Antisolvent‐Free Crystallization of All‐Inorganic Perovskites for Highly Efficient and Thermally Stable Solar Cells

Abstract All‐inorganic perovskites have emerged as promising photovoltaic materials due to their superior thermal stability compared to their heat‐sensitive hybrid organic–inorganic counterparts. In particular, CsPbI 2 Br shows the highest potential for developing thermally‐stable perovskite solar cells (PSCs) among all‐inorganic compositions. However, controlling the crystallinity and morphology of all‐inorganic compositions is a significant challenge. Here, a simple, thermal gradient‐ and antisolvent‐free method is reported to control the crystallization of CsPbI 2 Br films. Optical in situ characterization is used to investigate the dynamic film formation during spin‐coating and annealing to understand and optimize the evolving film properties. This leads to high‐quality perovskite films with micrometer‐scale grain sizes with a noteworthy performance of 17% (≈16% stabilized), fill factor (FF) of 80.5%, and open‐circuit voltage ( V OC ) of 1.27 V. Moreover, excellent phase and thermal stability are demonstrated even after extreme thermal stressing at 300 °C.

36 MATERIALS SCIENCE↗

Lignin-Based Low-Density Rigid Polyurethane/Polyisocyanurate Foams

In this paper, unmodified kraft softwood lignin was utilized to fully replace the petroleum-based polyol for the first time in low-density rigid polyurethane/polyisocyanurate (PUR/PIR) foam. The effects of different lignin incorporation levels (0, 25, 50, 75, and 100%) on foam properties were investigated by measuring foam’s reactivity, polyol viscosity (using a rheometer), apparent density, compression strength, closed cell content (using a gas pycnometer), thermal conductivity, fire resistance, and morphology (observed through SEM). All formulated lignin-based foams met the ASTM minimum requirements for type 1 rigid insulation foams. Remarkably, the foam made by replacing 100% of the petrochemical polyol with the commercially available kraft lignin demonstrated outstanding fire resistance performance, reducing the burn length by 127%.

09 BIOMASS FUELS↗

Less Is More: Oligomer Extraction and Hydrothermal Annealing Increase PDMS Adhesion Forces for Materials Studies and for Biology-Focused Microfluidic Applications

Cues in the micro-environment are key determinants in the emergence of complex cellular morphologies and functions. Primary among these is the presence of neighboring cells that form networks. For high-resolution analysis, it is crucial to develop micro-environments that permit exquisite control of network formation. This is especially true in cell science, tissue engineering, and clinical biology. We introduce a new approach for assembling polydimethylsiloxane (PDMS)-based microfluidic environments that enhances cell network formation and analyses. We report that the combined processes of PDMS solvent-extraction and hydrothermal annealing create unique conditions that produce high-strength bonds between solvent-extracted PDMS (E-PDMS) and glass—properties not associated with conventional PDMS. Extraction followed by hydrothermal annealing removes unbound oligomers, promotes polymer cross-linking, facilitates covalent bond formation with glass, and retains the highest biocompatibility. Herein, our extraction protocol accelerates oligomer removal from 5 to 2 days. Resulting microfluidic platforms are uniquely suited for cell-network studies owing to high adhesion forces, effectively corralling cellular extensions and eliminating harmful oligomers. We demonstrate the simple, simultaneous actuation of multiple microfluidic domains for invoking ATP- and glutamate-induced Ca 2+ signaling in glial-cell networks. These E-PDMS modifications and flow manipulations further enable microfluidic technologies for cell-signaling and network studies as well as novel applications.

36 MATERIALS SCIENCE↗

Quantifying the Relationship Between Microstructure and Performance in Gadolinium-Doped Ceria Infiltrated Ni/YSZ Symmetric Cells

Infiltration of mixed ionic/electronic conducting (MIEC) nanocatalysts into the anodes of solid oxide fuel cells (SOFCs) allow the hydrogen oxidation reaction (HOR) to occur at double-phase boundaries (DPBs), rather than being confined only to the triple phase boundaries (TPBs). In this research, we use a combination of cross-sectional scanning electron microscopy (SEM), three-dimensional (3-D) reconstruction, and electrochemical methods to characterize both baseline and gadolinium-doped ceria (GDC)-infiltrated symmetric cells, with the goal of establishing a comparison between the density of electrochemically active sites in uninfiltrated and GDC-infiltrated cells. Here, electrochemical impedance spectroscopy (EIS) and distribution of relaxation times (DRT) analysis showed GDC infiltration decreased the overall polarization of the anode by a factor of 8.78 X, and decreased the resistance associated with the reactions at the TPBs/DPBs by a factor of over 21 X. By quantifying expected GDC deposition morphology in the Ni/YSZ anode it is estimated that reactions occur in the baseline cell up to 84 nm from the active TPB lines.

36 MATERIALS SCIENCE↗

Linking structure to performance: Characterization of porous transport layers for high-pressure water electrolysis

Proton exchange membrane (PEM) water electrolysis is a promising technology to produce cost-efficient hydrogen. PEM electrolyzers offer a large current density range and the ability to operate at differential pressure which can be used to minimize both capital and operational expenditures. However, directly producing pressurized hydrogen at the cathode results in pushing the membrane against the anode porous transport layer (PTL). This can lead to detrimental effects, such as membrane deformation or ruptures, which depend on membrane properties as well as PTL material properties such as pore size, structure, and morphology. In this work, a range of sinter and felt-based commercial PTLs are evaluated for their contributions to the cell's electrochemical and H 2 crossover performance at cathode pressures up to 30 bar. X-ray tomography and post-operando optical microscopy are used to assess the morphology of the PTLs, and the PTL induced deformation experienced by the catalyst coated membrane (CCM), respectively. PTL samples with lower porosity were found to reduce both the cell voltage and the amount of H 2 permeating from the cathode to the anode exhaust, which was ascribed to improved catalyst layer contact and reduced membrane deformation, respectively. The best performing PTLs improved electrolyzer efficiency by ~1.5 kWh/kg H2 . Specifically, 1 kWh/kg H2 was gained due to reducing membrane deformation and decreasing H 2 crossover. The remainder 0.5 kWh/kg H2 were achieved by improving the electrical contact at the electrode/PTL interface which decreased cell voltage.

08 HYDROGEN↗

Mycosynthesis of Zinc Oxide Nanoparticles Exhibits Fungal Species Dependent Morphological Preference

Filamentous fungi can synthesize a variety of nanoparticles (NPs), a process referred to as mycosynthesis that requires little energy input, do not require the use of harsh chemicals, occurs at near neutral pH, and do not produce toxic byproducts. While NP synthesis involves reactions between metal ions and exudates produced by the fungi, the chemical and biochemical parameters underlying this process remain poorly understood. Here, the role of fungal species and precursor salt on the mycosynthesis of zinc oxide (ZnO) NPs is investigated. This data demonstrates that all five fungal species tested are able to produce ZnO structures that can be morphologically classified into i) well-defined NPs, ii) coalesced/dissolving NPs, and iii) micron-sized square plates. Further, species-dependent preferences for these morphologies are observed, suggesting potential differences in the profile or concentration of the biochemical constituents in their individual exudates. This data also demonstrates that mycosynthesis of ZnO NPs is independent of the anion species, with nitrate, sulfate, and chloride showing no effect on NP production. Finally, these results enhance the understanding of factors controlling the mycosynthesis of ceramic NPs, supporting future studies that can enable control over the physical and chemical properties of NPs formed through this “green” synthesis method.

59 BASIC BIOLOGICAL SCIENCES↗

Morphology engineering of iridium electrodes via modifying titanium substrates with controllable pillar structures for highly efficient oxygen evolution reaction

Nowadays, Ti is the well-chosen anode substrate material for proton exchange membrane electrolyzer cells (PEMECs) and modifications of the substrate surfaces are essential for the fabrication of highly efficient electrodes. Herein, we introduce the morphology engineering of Ir/Ti electrodes with different acid treatments of hydrochloric acid (HCl) and oxalic acid (OA), and the comparative benefits of these two acid treatment methods are studied from the aspects of their impacts on the morphology, interfacial contact resistance (ICR), and oxygen evolution reaction (OER) performances of resultant electrodes. Notably, compared to the flat surface from OA treatment, Ti substrates with the pillar structure could be successfully achieved via HCl etching. Further, the HCl and the oxalic acid (OA) treatments would reduce the interfacial contact resistance (ICR) to 15.2% and 5.5% of the pristine Ti substrate at 1.38 MPa, respectively. By iridium electrodeposition on Ti substrates, Ir/Ti electrodes with different catalyst loadings are fabricated. With similar low-loadings of about 0.05 mgIr cm –2 , an Ir/Ti electrode with HCl treated substrate exhibits a lower overpotential of ~283 mV at 10 mA cm –2 current density than 305 mV from OA treatment, due to the boosted reaction areas from HCl treatment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High Performance GaAs Solar Cells Grown at High Growth Rates by Atmospheric-Pressure Dynamic Hydride Vapor Phase Epitaxy

We report GaAs solar cells grown at rates exceeding 300 um/h by atmospheric-pressure dynamic hydride vapor phase epitaxy (D-HVPE). The surface morphology of the GaAs layers grown at those rates is smooth, with root mean square surface roughness of < 1.4 nm. We grew GaAs solar cells at rates from 35 - 309 um/h with negligible degradation in open circuit voltages (VOC), which ranged from 1.04 - 1.07 V. We showed the slight decrease in VOC is due to lack of doping optimization at higher growth rates. Deep level transient spectroscopy measurements showed low point defect densities that increases slightly with growth rate from 35 - 309 um/h. The low point defect concentrations and the high VOCs indicate that high material quality can be maintained at these extremely high growth rates, enabling the deposition of high efficiency cells in mere seconds instead of hours.

14 SOLAR ENERGY↗

Rapid assessment of beech leaf disease in Fagus sylvatica buds

Abstract The European beech (Fagus sylvatica) is threatened by the foliar nematodeLitylenchus crenataesubsp.mccannii(Lcm), the causal agent of beech leaf disease (BLD). Thus far, the majority of studies regarding BLD have focused on American beech (F. grandifolia). To better determine the impact of Lcm in buds of European beech, a total of 54 buds were collected from naturally symptomatic trees. Here, we characterized for the first time the bud scale morphology of two different cultivars ofF. sylvaticainfected with Lcm. Detailed observations of asymptomatic and symptomatic bud scales provided insight into the physical changes and arrangements of cells in the bud scale, shedding light on the dynamic processes occurring during Lcm infection. In addition, we evaluated the suitability of using the bud scale morphology for the early detection of BLD and Lcm in naturally infected buds. The distinct cellular arrangement of symptomatic bud scales cells (i.e., asymmetric pattern of enlarged cells) provides a rapid and visual, user‐friendly methodology to prematurely diagnose BLD symptoms within the buds, as well as the detection of associated nematodes.

Forestry↗

Working Principle of an Ionic Liquid Interlayer During Pressureless Lithium Stripping on Li 6.25 Al 0.25 La 3 Zr 2 O 12 (LLZO) Garnet‐Type Solid Electrolyte

Abstract Solid‐state‐batteries employing lithium metal anodes promise high theoretical energy and power densities. However, morphological instability occurring at the lithium/solid–electrolyte interface when stripping and plating lithium during cell cycling needs to be mitigated. Vacancy diffusion in lithium metal is not sufficiently fast to prevent pore formation at the interface above a certain current density during stripping. Applied pressure of several MPa can prevent pore formation, but this is not conducive to practical application. This work investigates the concept of ionic liquids as “self‐adjusting” interlayers to compensate morphological changes of the lithium anode while avoiding the use of external pressure. A clear improvement of the lithium dissolution process is observed as it is possible to continuously strip more than 70 μm lithium (i. e., 15 mAh cm −2 charge) without the need for external pressure during assembly and electrochemical testing of the system. The impedance of the investigated electrodes is analyzed in detail, and contributions of the different interfaces are evaluated. The conclusions are corroborated with morphology studies using cryo‐FIB‐SEM and chemical analysis using XPS. This improves the understanding of the impedance response and lithium stripping in electrodes employing liquid interlayers, acting as a stepping‐stone for future optimization.

Fuchs, Till↗

Tuning Catalyst Activation and Utilization Via Controlled Electrode Patterning for Low-Loading and High-Efficiency Water Electrolyzers

An anode electrode concept of thin catalyst-coated liquid/gas diffusion layers (CCLGDLs), by integrating Ir catalysts with Ti thin tunable LGDLs with facile electroplating in proton exchange membrane electrolyzer cells (PEMECs), is proposed. The CCLGDL design with only 0.08 mg Ir cm -2 can achieve comparative cell performances to the conventional commercial electrode design, saving ~97% Ir catalyst and augmenting a catalyst utilization to ~24 times. CCLGDLs with regulated patterns enable insight into how pattern morphology impacts reaction kinetics and catalyst utilization in PEMECs. A specially designed two-sided transparent reaction-visible cell assists the in situ visualization of the PEM/electrode reaction interface for the first time. Oxygen gas is observed accumulating at the reaction interface, limiting the active area and increasing the cell impedances. In this work, it is demonstrated that mass transport in PEMECs can be modified by tuning CCLGDL patterns, thus improving the catalyst activation and utilization. The CCLGDL concept promises a future electrode design strategy with a simplified fabrication process and enhanced catalyst utilization. Furthermore, the CCLGDL concept also shows great potential in being a powerful tool for in situ reaction interface research in PEMECs and other energy conversion devices with solid polymer electrolytes.

08 HYDROGEN↗

Imaging, understanding, and control of nanoscale materials transformations

The development of liquid cells for transmission electron microscopy has enabled breakthroughs in our ability to follow nanoscale structural, morphological, or chemical changes during materials growth and applications. Time-resolved high-resolution imaging and chemical analysis through liquids opened the opportunity to capture nanoscale dynamic processes of materials, including reaction intermediates and the transformation pathways. In this article, a series of work is highlighted with topics ranging from liquid cell developments to in situ studies of nanocrystal growth and transformations, dendrite formation, and suppression of lithium dendrites through in situ characterization of the solid–electrolyte interphase chemistry. The understanding garnered is expected to accelerate the discovery of novel materials for applications in energy storage, catalysis, sensors, and other functional devices.

36 MATERIALS SCIENCE↗

Colossal grain growth in Cd(Se,Te) thin films and their subsequent use in CdTe epitaxy by close-spaced sublimation

Many technologies deposit thin films on inexpensive substrates, resulting in small grains due to classic nucleation and grain growth theory. For example, state-of-the-art solar cells are made by depositing CdSeTe and CdTe layers on inexpensive glass coated with nanocrystalline transparent conducting oxides (TCOs), like SnO 2 . Characteristically, the grain size of these films is on the order of the film thickness, i.e. a few microns. CdTe small-grain films have poor electro-optical properties and require CdCl 2 passivation which fails to fully passivate grain boundaries, causes carrier compensation, and prevents implementing other II–VI alloys and materials to improve performance. Here, we present a method to increase grain size to 1 mm in CdSe x Te 1-x thin films deposited on glass/TCO substrates without CdCl 2 treatment. The colossal grain growth is driven by mechanisms distinct from classic nucleation, grain growth, and Ostwald ripening and only occurs at low selenium content (x ~ 0.1). We also demonstrate how these films can serve as templates for subsequent large-grain epitaxy of other compositions like CdTe, again without exposure to CdCl 2 . The results open new paths for thin film solar cell technology, and thin film devices in general.

36 MATERIALS SCIENCE↗

Highly Reversible Sodium Metal Battery Anodes via Alloying Heterointerfaces

As a promising pathway toward low-cost, long-duration energy storage, rechargeable sodium batteries are of increasing interest. Batteries that incorporate metallic sodium as anode promise a high theoretical specific capacity of 1166 mAh g –1 , and low reduction potential of –2.71 V. The high reactivity and poor electrochemical reversibility of sodium anodes render sodium metal anode (SMA) cells among the most challenging for practical implementation. Here, the failure mechanisms of Na anodes are investigated and the authors report that loss of morphological control is not the fundamental cause of failure. Rather, it is the inherently poor anchoring/root structure of electrodeposited Na to the electrode substrate that leads to poor reversibility and cell failure. Poorly anchored Na deposits are prone to break away from the current collector, producing orphaning and poor anode utilization. Thin metallic coatings in a range of chemistries are proposed and evaluated as SMA substrates. Based on thermodynamic and ion transport considerations, such substrates undergo reversible alloying reactions with Na and are hypothesized to promote good root growth—regardless of the morphology. Among the various options, Au stands out for its ability to support long Na anode lifetime and high reversibility (Coulombic Efficiency > 98%), for coating thicknesses in the range of 10–1000 nm. Finally, as a first step toward evaluating practical utility of the anodes, their performance in Na||SPAN cells with N:P ratio close to 1:1 is evaluated.

25 ENERGY STORAGE↗

Introducing a Phenyl End Group in the Inner Side Chains of A‐DA'D‐A Acceptors Enables High‐Efficiency Organic Solar Cells Processed with Nonhalogenated Solvent

Abstract Power conversion efficiency (PCE) of organic solar cells (OSCs) processed by nonhalogenated solvents is unsatisfactory due to the unfavorable morphology. Herein, two new small molecule acceptors (SMAs) Y6‐Ph and L8‐Ph are synthesized by introducing a phenyl end group in the inner side chains of the SMAs of Y6 and L8‐BO, respectively, for overcoming the excessive aggregation of SMAs in the long‐time film forming processed by nonhalogenated solvents. First, the effect of the film forming time on the aggregation property and photovoltaic performance of Y6, L8‐BO, Y6‐Ph, and L8‐Ph is studied by using the commonly used solvents: chloroform (CF) (rapid film forming process) and chlorobenzene (CB) (slow film forming process). It is found that Y6‐ and L8‐BO‐based OSCs exhibit a dramatic drop in PCE from CF‐ to CB‐processed devices owing to the large phase separation, while the Y6‐Ph and L8‐Ph based OSCs show obviously increased PCEs Furthermore, L8‐Ph‐based OSCs processed by nonhalogenated solvento‐xylene (o‐XY) achieved a high PCE of 18.40% with an FF of 80.11%. The results indicate that introducing a phenyl end group in the inner side chains is an effective strategy to modulate the morphology and improve the photovoltaic performance of the OSCs processed by nonhalogenated solvents.

Chemistry↗

Permissiveness and competition within and between Neurospora crassa syncytia

A multinucleate syncytium is a common growth form in filamentous fungi. Comprehensive functions of the syncytial state remain unknown, but it likely allows for a wide range of adaptations to enable filamentous fungi to coordinate growth, reproduction, responses to the environment, and to distribute nuclear and cytoplasmic elements across a colony. Indeed, the underlying mechanistic details of how syncytia regulate cellular and molecular processes spatiotemporally across a colony are largely unexplored. Here, we implemented a strategy to analyze the relative fitness of different nuclear populations in syncytia of Neurospora crassa , including nuclei with loss-of-function mutations in essential genes, based on production of multinucleate asexual spores using flow cytometry of pairings between strains with differentially fluorescently tagged nuclear histones. The distribution of homokaryotic and heterokaryotic asexual spores in pairings was assessed between different auxotrophic and morphological mutants, as well as with strains that were defective in somatic cell fusion or were heterokaryon incompatible. Mutant nuclei were compartmentalized into both homokaryotic and heterokaryotic asexual spores, a type of bet hedging for maintenance and evolution of mutational events, despite disadvantages to the syncytium. However, in pairings between strains that were blocked in somatic cell fusion or were heterokaryon incompatible, we observed a “winner-takes-all” phenotype, where asexual spores originating from paired strains were predominantly one genotype. These data indicate that syncytial fungal cells are permissive and tolerate a wide array of nuclear functionality, but that cells/colonies that are unable to cooperate via syncytia formation actively compete for resources.

59 BASIC BIOLOGICAL SCIENCES↗