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At least 109 records · Page 6

Crystal structure and ion conductivity of a new mixed-anion phosphate LiMg{sub 3}(PO{sub 4})P{sub 2}O{sub 7}

A new lithium-containing phosphate, LiMg{sub 3}(PO{sub 4})P{sub 2}O{sub 7}, was prepared by a solid-state reaction, and it was characterized by an ab initio structure determination method on the basis of synchrotron powder X-ray diffraction data. LiMg{sub 3}(PO{sub 4})P{sub 2}O{sub 7} was found to be orthorhombic (space group Pnma) with lattice parameters a=9.0387(1) Å, b=10.6072(1) Å, c=8.3065(1) Å, and V=796.39(1) Å{sup 3}. The structure features infinite [Mg{sub 3}O{sub 10}]{sub ∞} layers that are parallel to the bc plane and that are interconnected along the a axis by PO{sub 4} and P{sub 2}O{sub 7} groups. The [Mg{sub 3}O{sub 10}]{sub ∞} layer contains Mg{sub 3}O{sub 14} trimers that are formed by three edge-shared MgO{sub 6} octahedra. The PO{sub 4} and P{sub 2}O{sub 7} groups are located alternatively between [Mg{sub 3}O{sub 10}]{sub ∞} layers. This gives rise to a three-dimensional framework that contains large tunnels along the directions [1 0 0] and [0 1 0]; the Li{sup +} ions are stabilized in these tunnels. AC impedance spectroscopy shows that LiMg{sub 3}(PO{sub 4})P{sub 2}O{sub 7} has an ionic conductivity of 3.40×10{sup −5} S cm{sup −1} at 769 K, with an activation energy of 1.17 eV. - Graphical abstract: Polyhedral view of LiMg3(PO4)P2O7. Li+ ions are represented by orange spheres, MgO6 groups by octahedra, and PO4 groups by tetrahedra. - Highlights: • New compound LiMg{sub 3}(PO{sub 4})P{sub 2}O{sub 7} is reported. • The crystal structure is investigated by synchrotron XRD analysis. • The structure features [Mg{sub 3}O{sub 10}]{sub ∞} layers with interconnecting PO{sub 4} and P{sub 2}O{sub 7} groups. • Correlation between the crystal structure and ionic conductivity is discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Lithium-ion battery physics and statistics-based state of health model

A pseudo-2d model using COMSOL Multiphysics® software is developed to simulate performance and performance degradation of Li-ion batteries consisting of layered and olivine cathodes with graphite anode when subjected to peak shaving grid service. Multiple degradation pathways are considered, including solid electrolyte interphase (SEI) formation and breakdown at the anode, cathode dissolution and its synergistic effect on SEI formation at the anode. The model is validated by simulating commercial cylindrical cell performance. A global model is developed to simulate performance across all chemistries, along with individual chemistry models using global model parameters as initial values. There is good agreement between these models for various optimization parameters such as SEI equilibrium potential, cathode dissolution exchange current density, solvent diffusivity in the SEI and SEI ionic conductivity. To circumvent time constraints related to the COMSOL model, a 0d global model is developed which fits data well and provides more clarity on differences in cathode dissolution exchange current density. Again, good agreement for various optimization parameters is obtained among the COMSOL global & individual chemistry models and the 0-d model. The lessons learned from the physics-based model is used to develop a top down statistics-based model using current, voltage and anode volumetric change per mole lithium intercalated, along with their interactions as degradation predictors. This model predicts out of sample degradation for multiple grid services and electric vehicle drive cycle with high accuracy and provides the pathway to develop an efficient battery management system combining machine learning and findings from physics-based computationally intensive algorithms.

Crawford, Aladsair J.↗

Local structure of Ni 80 X 20 (X: Cr, Mn, Pd) solid-solution alloys and its response to ion irradiation

In this work, the local structure of Ni 80 X 20 (X: Cr, Mn, Pd) solid-solution alloys was investigated with x-ray absorption and total scattering x-ray diffraction methods. Atomic pair distribution function (PDF) analysis indicated that the local lattice distortion is strongly relevant to the atomic size mismatch, and the local lattice distortion in Ni80Pd20 alloy is obviously larger than that in other solid-solution alloys. The bond length of different atomic pairs was derived from the fitting of extended x-ray absorption fine structure spectra. Quantitative analysis of the local bonding environment in Ni 80 Cr 20 during Ni ion irradiation suggested that Cr atoms tend to form clusters in Ni 80 Cr 20 with the increase of ion dose.

36 MATERIALS SCIENCE↗

Polarized {sup 3}He{sup −} ion source with hyperfine state selection

High beam polarization is essential to the scientific productivity of a collider. Polarized {sup 3}He ions are an essential part of the nuclear physics programs at existing and future ion-ion and electron-ion colliders such as BNL's RHIC and eRHIC and JLab's ELIC. Ion sources with performance exceeding that achieved today are a key requirement for the development of these next generation high-luminosity high-polarization colliders. The development of high-intensity high-brightness arc-discharge ion sources at the Budker Institute of Nuclear Physics (BINP) has opened up an opportunity for realization of a new type of a polarized {sup 3}He{sup −} ion source. This report discusses a polarized {sup 3}He{sup −} ion source based on the large difference of extra-electron auto-detachment lifetimes of the different {sup 3}He{sup −} ion hyperfine states. The highest momentum state of 5/2 has the largest lifetime of τ ∼ 350 µs while the lower momentum states have lifetimes of τ ~ 10 µs. By producing {sup 3}He{sup −} ion beam composed of only the |5/2, ±5/2> hyperfine states and then quenching one of the states by an RF resonant field, {sup 3}He{sup −} beam polarization of 90% can be achieved. Such a method of polarized {sup 3}He{sup −} production has been considered before; however, due to low intensities of the He{sup +} ion sources existing at that time, it was not possible to produce any interesting intensity of polarized {sup 3}He{sup −} ions. The high-brightness arc-discharge ion source developed at BINP can produce a high-brightness {sup 3}He{sup +} beam with an intensity of up to 2 A allowing for selection of up to ∼1-4 mA of {sup 3}He{sup −} ions with ∼90% polarization. The high gas efficiency of an arc-discharge source is important due to the high cost of {sup 3}He gas. Some features of such a PIS as well as prototype designs are considered. An integrated {sup 3}He{sup −} ion source design providing high beam polarization could be prepared using existing BNL equipment with incorporation of new designs of the 1) arc discharge plasma generator, 2) extraction system, 3) charge exchange jet, and 4) magnetic separation system.

43 PARTICLE ACCELERATORS↗

Lithium formate ion clusters formation during electrospray ionization: Evidence of magic number clusters by mass spectrometry and ab initio calculations

Small cationic and anionic clusters of lithium formate were generated by electrospray ionization and their fragmentations were studied by tandem mass spectrometry (collision-induced dissociation with N{sub 2}). Singly as well as multiply charged clusters were formed in both positive and negative ion modes with the general formulae, (HCOOLi){sub n}Li{sup +}, (HCOOLi){sub n}Li{sub m}{sup m+}, (HCOOLi){sub n}HCOO{sup −}, and (HCOOLi){sub n}(HCOO){sub m}{sup m−}. Several magic number cluster (MNC) ions were observed in both the positive and negative ion modes although more predominant in the positive ion mode with (HCOOLi){sub 3}Li{sup +} being the most abundant and stable cluster ion. Fragmentations of singly charged positive clusters proceed first by the loss of a dimer unit ((HCOOLi){sub 2}) followed by the loss of monomer units (HCOOLi) although the former remains the dominant dissociation process. In the case of positive cluster ions, all fragmentations lead to the magic cluster (HCOOLi){sub 3}Li{sup +} as the most abundant fragment ion at higher collision energies which then fragments further to dimer and monomer ions at lower abundances. In the negative ion mode, however, singly charged clusters dissociated via sequential loss of monomer units. Multiply charged clusters in both positive and negative ion modes dissociated mainly via Coulomb repulsion. Quantum chemical calculations performed for smaller cluster ions showed that the trimer ion has a closed ring structure similar to the phenalenylium structure with three closed rings connected to the central lithium ion. Further additions of monomer units result in similar symmetric structures for hexamer and nonamer cluster ions. Thermochemical calculations show that trimer cluster ion is relatively more stable than neighboring cluster ions, supporting the experimental observation of a magic number cluster with enhanced stability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hydrodynamic description of an unmagnetized plasma with multiple ion species. I. General formulation

A generalization of the Braginskii ion fluid description [S. I. Braginskii, Sov. Phys. JETP 6, 358 (1958)] to the case of an unmagnetized collisional plasma with multiple ion species is presented. An asymptotic expansion in the ion Knudsen number is used to derive the individual ion species continuity, as well as the total ion mass density, momentum, and energy evolution equations accurate through the second order. Expressions for the individual ion species drift velocities with respect to the center of mass reference frame, as well as for the total ion heat flux and viscosity, which are required to close the fluid equations, are evaluated in terms of the first-order corrections to the lowest order Maxwellian ion velocity distribution functions. A variational formulation for evaluating such corrections and its relation to the plasma entropy are presented. Employing trial functions for the corrections, written in terms of expansions in generalized Laguerre polynomials, and maximizing the resulting functionals produces two systems of linear equations (for “vector” and “tensor” portions of the corrections) for the expansion coefficients. A general matrix formulation of the linear systems as well as expressions for the resulting transport fluxes are presented in forms convenient for numerical implementation. The general formulation is employed in the companion paper [A. N. Simakov and K. Molvig, Hydrodynamic description of an unmagnetized plasma with multiple ion species. II. Two and three ion species plasmas, submitted to Phys. Plasmas (2015)] to evaluate the individual ion drift velocities and the total ion heat flux and viscosity for specific cases of two and three ion species plasmas.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Multidiagnostic analysis of ion dynamics in ultrafast laser ablation of metals over a large fluence range

The dynamics of ions in ultrafast laser ablation of metals is studied over fluences ranging from the ablation threshold up to ≈75 J/cm{sup 2} by means of three well-established diagnostic techniques. Langmuir probe, Faraday cup, and spectrally resolved intensified charge coupled device imaging simultaneously monitored the ions produced during ultrafast laser ablation of a pure copper target with 800 nm, ≈50 fs, Ti: Sapphire laser pulses. The fluence dependence of ion yield is analyzed, resulting in the observance of three different regimes. The specific ion yield shows a maximum at about 4–5 J/cm{sup 2}, followed by a gradual reduction and a transition to a high-fluence regime above ≈50 J/cm{sup 2}. The fluence dependence of the copper ions angular distribution is also analyzed, observing a gradual increase in forward-peaking of Cu ions for fluences up to ≈10 J/cm{sup 2}. A broader ion component is observed at larger angles for fluences larger than ≈10 J/cm{sup 2}. Finally, an experimental characterization of the ionic angular distribution for several metallic targets (Mg, Al, Cr, Fe, Cu, and W) is carried out at a relatively high fluence of ≈66 J/cm{sup 2}. Interestingly, the ion emission from the volatile metals shows a narrow, forward-peaked distribution, and a high peak ion yield compared to the refractory metals. Moreover, the width of ionic angular distributions presents a striking correlation with the peak ion yield.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Tandem Mass Spectrometry and Ion Mobility Reveals Structural Insight into Eicosanoid Product Ion Formation

Ion mobility measurements of product ions were used to characterize the collisional cross section (CCS) of various complex lipid [M-H]{sup −} ions using traveling wave ion mobility mass spectrometry (TWIMS). TWIMS analysis of various product ions derived after collisional activation of mono- and dihydroxy arachidonate metabolites was found to be more complex than the analysis of intact molecular ions and provided some insight into molecular mechanisms involved in product ion formation. The CCS observed for the molecular ion [M-H]{sup −} and certain product ions were consistent with a folded ion structure, the latter predicted by the proposed mechanisms of product ion formation. Unexpectedly, product ions from [M-H-H{sub 2}O-CO{sub 2}]{sup −} and [M-H-H{sub 2}O]{sup −} displayed complex ion mobility profiles suggesting multiple mechanisms of ion formation. The [M-H-H{sub 2}O]{sup −} ion from LTB{sub 4} was studied in more detail using both nitrogen and helium as the drift gas in the ion mobility cell. One population of [M-H-H{sub 2}O]{sup −} product ions from LTB{sub 4} was consistent with formation of covalent ring structures, while the ions displaying a higher CCS were consistent with a more open-chain structure. Using molecular dynamics and theoretical CCS calculations, energy minimized structures of those product ions with the open-chain structures were found to have a higher CCS than a folded molecular ion structure. The measurement of product ion mobility can be an additional and unique signature of eicosanoids measured by LC-MS/MS techniques. .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reducing ion diffusion at atmospheric pressure through intermingled positive and negative ions

Increasing ion molecule reaction times for ambient ionization techniques can increase sensitivity of detection. Longer reaction times result in an increase in analyte signal relative to the reactant ion signal, however with a subsequent decrease in the total ion intensity. This loss in the total number of ions reaching the detector limits the extent to which increased reaction time can improve detection in practical applications. In this study ion loss was measured using either electric fields or gas flow to control ion transit time. Ion transit times ranged from 40 ms to 8s, which resulted in ion densities ranging from 5 x 10 6 to 2 x 10 4 ions/cm 3 , respectively. These results provide insights into practical reaction time limitations or experimental boundaries when exploring sensitivity enhancements in ambient ionization. When exploring longer reaction times with an atmospheric flow tube coupled to a mass spectrometer (AFT-MS), an additional corona discharge ionization source of the same polarity was added in an attempt to increase total ion signal, but no improvement in signal was observed. This observation suggested that there was a maximum ion density being reached by the corona discharge that could not be increased by adding more of the same polarity ions. A hypothesis was that intermingling both polarities of ions would reduce ion loss and increase the measured ion signal. When two corona discharge sources—one each of positive and negative polarity—were used simultaneously in an AFT-MS, the total ion signal of either polarity measured by the MS was approximately double the current from a single corona discharge source. An increase in the negative ion signal was also observed when ~10 parts-per-trillion vapor levels of an explosive (RDX) were introduced. In this case both the nitrate reactant ions and the RDX signal more than doubled with the addition of a corona discharge source producing positive ions. When intermingling positive and negative ions, an increase in ion current was also observed when the AFT was coupled directly to a Faraday detector or to an ion mobility spectrometer. This was the first demonstration of interfacing the AFT to an IMS. The observations and developments from this work will help in creating more portable instruments with improved sensitivity for detection of chemicals.

47 OTHER INSTRUMENTATION↗