Regulating the Hidden Solvation‐Ion‐Exchange in Concentrated Electrolytes for Stable and Safe Lithium Metal Batteries
Not Available
25 ENERGY STORAGE↗
Engineering topics
Sun, Hui
Publications and source records attributed to Sun, Hui.
High rate and long cycle life in Li-O 2 batteries with highly efficient catalytic cathode configured with Co 3 O 4 nanoflower
The reaction mechanism of non-aqueous Li-O 2 batteries is based on the deposition and decomposition of Li 2 O 2 . The polarization of Li-O 2 batteries can be rapidly increased by operation under a high rate condition, resulting in the early capacity fade of the cells. Therefore, a well-designed catalyst with a unique structure and excellent catalytic ability is an important way to boost the round-trip performance of Li-O 2 batteries, especially under high current density. In this work, a unique nanoflower structure assembled with Co 3 O 4 nanosheets is synthesized by using 2-methylimidazole (2-MIM) as a structural directing agent. X-ray photoelectron spectroscopy (XPS) and Raman spectra reveal abundant oxygen vacancies on the surface of the Co 3 O 4 nanoflower, which are beneficial for oxygen reduction and evolution reactions and long round-trip lifetime. Density functional theory results demonstrate that Co 3 O 4 catalyst with oxygen vacancies could promote the wetting of Li 2 O 2 on substrate and formation of a Li 2 O 2 nanofilm, thereby boosting the discharge capacity of Li-O 2 batteries. On account of the synergistic effect of abundant oxygen vacancies, the unique structure, and excellent oxygen evolution reaction, Co 3 O 4 nanoflower-based cells could deliver ultralong lifetime of 276 and 248 cycles with a discharge capacity of 1000 mAh g(-1) under charge/discharge current densities of 0.5 A g -1 and 1 A g -1 , respectively. Finally, this study has shed light on a new strategy for catalyst preparation for long lifetime Li-O 2 batteries.
25 ENERGY STORAGE↗
Solid-State Lithium/Selenium–Sulfur Chemistry Enabled via a Robust Solid-Electrolyte Interphase
Lithium/selenium-sulfur batteries have recently received considerable attention due to their relatively high specific capacities and high electronic conductivity. Different from the traditional encapsulation strategy for suppressing the shuttle effect, an alternative approach to directly bypass polysulfide/polyselenide formation via rational solid-electrolyte interphase (SEI) design is demonstrated here. It is found that the robust SEI layer that in situ forms during charge/discharge via interplay between rational cathode design and optimal electrolytes could enable solid-state (de)lithiation chemistry for selenium-sulfur cathodes. Hence, Se-doped S 22.2 Se/Ketjenblack cathodes can attain a high reversible capacity with minimal shuttle effects during long-term and high rate cycling. Moreover, the underlying solid-state (de)lithiation mechanism, as evidenced by in situ 7 Li NMR and in operando synchrotron X-ray probes, further extends the optimal sulfur confinement pore size to large mesopores and even macropores that have been long considered as inferior sulfur or selenium host materials, which play a crucial role in developing high volumetric energy density batteries. It is expected that the findings in this study will ignite more efforts to tailor the compositional/structure characteristics of the SEI layers and the related ionic transport across the interface by electrode structure, electrolyte solvent, and electrolyte additive screening.
(de)lithiation chemistry↗
Bacterial endosymbionts influence host sexuality and reveal reproductive genes of early divergent fungi
Many heritable mutualisms, in which beneficial symbionts are transmitted vertically between host generations, originate as antagonisms with parasite dispersal constrained by the host. Only after the parasite gains control over its transmission is the symbiosis expected to transition from antagonism to mutualism. Here, we explore this prediction in the mutualism between the fungus Rhizopus microsporus ( Rm , Mucoromycotina) and a beta-proteobacterium Burkholderia , which controls host asexual reproduction. We show that reproductive addiction of Rm to endobacteria extends to mating, and is mediated by the symbiont gaining transcriptional control of the fungal ras2 gene, which encodes a GTPase central to fungal reproductive development. We also discover candidate G-protein-coupled receptors for the perception of trisporic acids, mating pheromones unique to Mucoromycotina. Our results demonstrate that regulating host asexual proliferation and modifying its sexual reproduction are sufficient for the symbiont’s control of its own transmission, needed for antagonism-to-mutualism transition in heritable symbioses. These properties establish the Rm-Burkholderia symbiosis as a powerful system for identifying reproductive genes in Mucoromycotina.
59 BASIC BIOLOGICAL SCIENCES↗
Probing the Energetics of Molecule–Material Interactions at Interfaces and in Nanopores
During the past decades, advances in interfacial chemistries at the molecular level are shaping our world by playing crucial roles in balancing global scale energy crisis and critical environmental concerns. However, systematic investigations into the binding energies, site distribution and their correlation with the molecular-level surface assemblages and structures at interfaces and in nanopores are rarely documented. In this review, we summarize a set of systematic calorimetric studies on surface energetics we performed during the last decade. These studies demonstrate how thermochemistry can reveal crucial energetic insights into a series of molecule – material interactions relevant to a number of applications, including carbon capture and sequestration, energy production, sustainable chemical processing, catalysis, and nanogeoscience. Calorimetric methodologies developed and applied include direct gas adsorption calorimetry, nearroom temperature solvent immersion/solution calorimetry and high temperature oxide melt solution calorimetry. Using these highly unique techniques, we reveal the thermodynamic complexity of carbon dioxide capture on metal – organic framework (MOF) sorbents with built-in and grafted nucleophilic functional groups (-OH and -NH2). These studies suggest that carbon dioxide adsorption on functionalized MOFs is a complex process involving multiple thermodynamic factors, as reflected by changes in surface phase and structure, chemical bonding and degree of disorder with varying temperature and gas loading. The fundamental insights obtained may help optimize the design, synthesis and application of MOF-based carbon dioxide sorbents for carbon capture and sequestration. In parallel, we also explore the energetics of interaction and competition between small molecules (water, carbon dioxide, methane, simple and complex organics) and inorganic materials (calcite, silica, zirconia, zeolites, mesoporous frameworks, alumina, and uranium), at interfaces and in nanopores. Combined with spectroscopic, diffraction, electron microscopic and computational techniques, the energetics of gas/liquid – solid interactions can be correlated with specific bonds, molecular configurations and nanostructures. Although the energetics evolves continuously from weak association to strong bonding to classical capping, distinct regions of rapidly changing stepwise energetics often separate the different regimes. These phenomena are closely related to the properties of inorganic material surfaces (hydrophobicity and acidity/basicity), the framework architectures, and the chemical nature of adsorbate molecules. These direct thermodynamic insights reinforce our understanding of complex small molecule – inorganic material interactions important to multiple disciplines of chemical engineering, materials science, nanogeoscience and environmental technology, including heterogeneous catalysis, molecular separation, material design and synthesis, biomineralization, contaminant and nutrient transport, carbonate formation, and water – organic competitions on material/mineral surfaces.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Magnetar Central Engine and Possible Gravitational Wave Emission of Nearby Short GRB 160821B
GRB 160821B is a short gamma-ray burst (SGRB) at redshift z = 0.16, with a duration less than 1 s and without any “extended emission” detected up to more than 100 s in both Swift /BAT and Fermi /GBM bands. An X-ray plateau with a sharp drop 180 s after the BAT trigger was observed with Swift /XRT. No supernova or kilo-nova signature was detected. Assuming the central engine of this SGRB is a recently born supra-massive magnetar, we can explain the SGRB as jet radiation and its X-ray plateau as the internal energy dissipation of the pulsar wind as it spins down. We constrain its surface magnetic field to B {sub p} < 3.12 × 10{sup 16} G and initial spin period to P{sub 0} < 8.5 × 10{sup −3} s. Its equation of state is consistent with the GM1 model with M{sub TOV} ∼ 2.37 M {sub ⊙} and ellipticity ϵ < 0.07. Its gravitational wave (GW) radiation may be detectable with the future Einstein Telescope, but is much weaker than the current detectability limit of Advanced LIGO. The GW radiation of such an event would be detectable by Advanced LIGO if it occurred at a distance of 100 Mpc ( z = 0.023).
79 ASTRONOMY AND ASTROPHYSICS↗
X-ray counterpart of gravitational waves due to binary neutron star mergers: light curves, luminosity function, and event rate density
Zhang proposed a type of GRB-less X-ray transient associated with double neutron star (NS–NS) mergers under the conjecture of a rapidly spinning magnetar merger product with the line of sight off the short gamma-ray burst (GRB) jet. We investigate possible light curves of these transients by considering different observers’ viewing angles. We perform Monte Carlo simulations to calculate the peak luminosity function (LF) and event rate density of these X-ray transients. By considering that a fraction of massive neutron stars may be supra-massive and later collapse into black holes after spinning down, we investigate how the predicted LF depends on the equation of state (EoS) of the central object and the geometry of the system. In general, the LF can be fit by two log-normal distributions peaking around 10{sup 46.4} and 10{sup 49.6} erg s{sup −1}, corresponding to the trapped and free zones, respectively. For the majority of the EoS models, the current non-detection is consistent with having a free zone solid angle, at most a few times the solid angle of the short GRB jet. The event rate density of these X-ray transients is around a few tens of Gpc{sup −3} yr{sup −1} for luminosity above 10{sup 45} erg s{sup −1}. We predict that future X-ray telescopes (such as Einstein Probe) with sensitivity ∼10{sup −11} erg s{sup −1} cm{sup −2} would detect as many as several tens of such transients per year per steradian. Within 200 Mpc, the aLIGO average range for NS–NS mergers, the estimated event rate of these transients is about 1 transient per year all sky.
79 ASTRONOMY AND ASTROPHYSICS↗
Comparative genomics of biotechnologically important yeasts
Significance The highly diverse Ascomycete yeasts have enormous biotechnological potential. Collectively, these yeasts convert a broad range of substrates into useful compounds, such as ethanol, lipids, and vitamins, and can grow in extremes of temperature, salinity, and pH. We compared 29 yeast genomes with the goal of correlating genetics to useful traits. In one rare species, we discovered a genetic code that translates CUG codons to alanine rather than canonical leucine. Genome comparison enabled correlation of genes to useful metabolic properties and showed the synteny of the mating-type locus to be conserved over a billion years of evolution. Our study provides a roadmap for future biotechnological exploitations.
59 BASIC BIOLOGICAL SCIENCES↗
Stochastic level-set variational implicit-solvent approach to solute-solvent interfacial fluctuations
Recent years have seen the initial success of a variational implicit-solvent model (VISM), implemented with a robust level-set method, in capturing efficiently different hydration states and providing quantitatively good estimation of solvation free energies of biomolecules. The level-set minimization of the VISM solvation free-energy functional of all possible solute-solvent interfaces or dielectric boundaries predicts an equilibrium biomolecular conformation that is often close to an initial guess. In this work, we develop a theory in the form of Langevin geometrical flow to incorporate solute-solvent interfacial fluctuations into the VISM. Such fluctuations are crucial to biomolecular conformational changes and binding process. We also develop a stochastic level-set method to numerically implement such a theory. We describe the interfacial fluctuation through the “normal velocity” that is the solute-solvent interfacial force, derive the corresponding stochastic level-set equation in the sense of Stratonovich so that the surface representation is independent of the choice of implicit function, and develop numerical techniques for solving such an equation and processing the numerical data. We apply our computational method to study the dewetting transition in the system of two hydrophobic plates and a hydrophobic cavity of a synthetic host molecule cucurbit[7]uril. Numerical simulations demonstrate that our approach can describe an underlying system jumping out of a local minimum of the free-energy functional and can capture dewetting transitions of hydrophobic systems. In the case of two hydrophobic plates, we find that the wavelength of interfacial fluctuations has a strong influence to the dewetting transition. In addition, we find that the estimated energy barrier of the dewetting transition scales quadratically with the inter-plate distance, agreeing well with existing studies of molecular dynamics simulations. Our work is a first step toward the inclusion of fluctuations into the VISM and understanding the impact of interfacial fluctuations on biomolecular solvation with an implicit-solvent approach.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Isovalent substitutes play in different ways: Effects of isovalent substitution on the thermoelectric properties of CoSi{sub 0.98}B{sub 0.02}
Boron-added CoSi, CoSi{sub 0.98}B{sub 0.02}, possesses a very high thermoelectric power factor of 60 μW cm{sup −1} K{sup −2} at room temperature, which is among the highest power factors that have ever been reported for near-room-temperature thermoelectric applications. Since the electrical properties of this material have been tuned properly, isovalent substitution for its host atoms is intentionally employed to reduce the lattice thermal conductivity while maintaining the electronic properties unchanged. In our previous work, the effect of Rh substitution for Co atoms on the thermoelectric properties of CoSi{sub 0.98}B{sub 0.02} has been studied. Here, we present a study of the substitution of Ge for Si atoms in this compound. Even though Ge and Rh are isovalent with their corresponding host atoms, they play different roles in determining the electrical and thermal transport properties. Through the evaluation of the lattice thermal conductivity by the Debye approximation and the comparison between the high-temperature Seebeck coefficients, we propose that Rh substitution leads to a further overlapping of the conduction and the valence bands, while Ge substitution only shifts the Fermi level upward into the conduction band. Our results show that the influence of isovalent substitution on the electronic structure cannot be ignored when the alloying method is used to improve thermoelectric properties.
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
Energetics of alkali and alkaline earth ion-exchanged zeolite A
Alkali and alkaline earth ion-exchanged zeolite A samples were synthesized in aqueous exchange media. They were thoroughly studied by powder X-ray diffraction (XRD), electron microprobe (EMPA), thermogravimetric analysis and differential scanning calorimetry (TG-DSC), and high temperature oxide melt solution calorimetry. The hydration energetics and enthalpies of formation of these zeolite A materials from constituent oxides were determined. Specifically, the hydration level of zeolite A has a linear dependence on the average ionic potential ( Z/r ) of the cation, from 0.894 (Rb-A) to 1.317 per TO 2 (Mg-A). The formation enthalpies from oxides (25 °C) range from –93.71 ± 1.77 (K-A) to –48.02 ± 1.85 kJ/mol per TO 2 (Li-A) for hydrated alkali ion-exchanged zeolite A, and from –47.99 ± 1.20 (Ba-A) to –26.41 ± 1.71 kJ/mol per TO 2 (Mg-A) for hydrated alkaline earth ion-exchanged zeolite A. As a result, the formation enthalpy from oxides generally becomes less exothermic as Z/r increases, but a distinct difference in slope is observed between the alkali and the alkaline earth series.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Dielectric, ferroelectric, and thermodynamic properties of silicone oil modified PVDF films for energy storage application
Silicone oil modified poly(vinylidene fluoride-co-hexafluoropropylene) (P(VDF-HFP)) films were fabricated by the blending, casting, and hot-molding methods. The dielectric constant was increased for the 7.4 wt. % and 17.0 wt. % silicone oil modified P(VDF-HFP) films, while the dielectric loss for all blend films are decreased. D-E loops of 7.4 wt. % and 17.0 wt. % silicone oil modified P(VDF-HFP) films become slimmer than the pristine P(VDF-HFP) films. The maximum discharged energy density of 10.3 J/cm{sup 3} was obtained in 7.4 wt. % silicone oil modified P(VDF-HFP) films at the external electric field of 398 kV/mm. The Gibbs energy, miscibility, and phase behavior of binary mixture of P(VDF-HFP) silicone oil were investigated using molecular simulations and the extended Flory–Huggins model revealing favorable interactions and compatibility between P(VDF-HFP) and silicone oil.
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
Interplay of confinement and surface energetics in the interaction of water with a metal–organic framework
Here, the enthalpy of water adsorption (Δh) on the metal–organic framework (MOF) HKUST-1 has been determined directly by calorimetry. The most exothermic value of Δh [–119.4 ± 0.5 kJ/(mol of water)] occurs at zero coverage and perhaps represents water confinement in the smallest (4-Å) cages. An intermediate Δh value of –50.2 ± 1.8 kJ/(mol of water) at higher loading probably corresponds to the binding of water on the available Cu nodes and subsequent filling of the largest (11-Å) pores. The weakest interactions take place in the medium (10-Å) cages, showing weak inclusion of water clusters in a limited hydrophobic environment. By combining ethanol adsorption calorimetry, mathematical analysis of the slope of the water adsorption isotherm, and the differential enthalpy of water adsorption curve, we are able not only to develop an approach to separate energetically multistage guest–host interactions in complex MOF architectures but also to distinguish a sequence of interactions with very similar energetic effects.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Supported single Au(III) ion catalysts for high performance in the reactions of 1,3-dicarbonyls with alcohols
Abstract not provided
Gao, Daowei↗
Improvement of the electrical contact resistance at rough interfaces using two dimensional materials
Reducing the electronic contact resistance at the interfaces of nanostructured materials is a major goal for many kinds of planar and three dimensional devices. In this work, we develop a method to enhance the electronic transport at rough interfaces by inserting a two dimensional flexible and conductive graphene sheet. We observe that an ultra-thin graphene layer with a thickness of 0.35 nm can remarkably reduce the roughness of a sample in a factor of 40%, avoiding the use of thick coatings, leading to a more homogeneous current flow, and extraordinarily increasing the total current compared to the graphene-free counterpart. Due to its simplicity and performance enhancement, this methodology can be of interest to many interface and device designers.
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗