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At least 19 records

Comparison of the effects of couplings to breakup channels in reactions induced by {sup 6}Li and {sup 6}He on the same {sup 64}Zn target

The experimental elastic scattering angular distributions for the weakly bound nuclei {sup 6,7}Li and for the halo nucleus {sup 6}He on the same {sup 64}Zn target at several energies around the Coulomb barrier were measured at the Laboratori Nazionali del Sud (LNS, Italy) and at the Cyclotron Research Center, Louvain La Neuve (Belgium), respectively. The measured elastic scattering angular distributions of these three systems at the same center of mass energy have been compared. The experimental data of the {sup 6,7}Li+ {sup 64}Zn systems have been analyzed within the CDCC method, while the {sup 6}He+{sup 64}Zn data have been compared with both both CDCC and CRC calculations.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Large electron screening effect in different environments

Electron screening effect was studied in the {sup 1}H({sup 7}Li,α){sup 4}He, {sup 1}H({sup 11}B,α){sup 4}He and {sup 1}H({sup 19}F,αγ){sup 16}O reactions in inverse kinematics on different hydrogen implanted targets. Results show large electron screening potentials strongly dependent on the proton number Z of the projectile.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Prediction of neutron production and energy spectrum by the inverse kinematic reaction between an incident 7 Li 3+ beam and a proton target in PHITS

A neutron source using the inverse kinematic reaction between lithium and proton, p( 7 Li, n) 7 Be, achieves forward-directed neutrons, potentially enhancing neutron yield in the forward direction. Despite the advantage, no evaluated-cross-section data for this reaction can be used in Monte Carlo simulation codes, such as PHITS. To solve this problem, this study aims to evaluate the applicability of the user-defined cross-section data, Frag data, for p ( 7 Li, n) 7 Be in PHITS. The simulations reproduced collisions between 7 Li 3+ ions and polypropylene targets. The Frag data was edited based on the JENDL-5 by utilizing the two-body collision kinematics. The neutron yield and angular distribution were investigated in the simulation. As a result, the forward neutron convergence with a reasonable neutron yield and energy spectrum was observed. The expected neutron yield in the forward 1-steradian area is 2.46 × 10 10 n/s when lithium-ion energy and current are 16.45 MeV and 0.1 mA.

43 PARTICLE ACCELERATORS↗

New Thermonuclear Rate of 7 Li(d,n)2 4 He Relevant to the Cosmological Lithium Problem

Accurate 7 Li(d,n)2 4 He thermonuclear reaction rates are crucial for precise prediction of the primordial abundances of lithium and beryllium and to probe the mysteries beyond fundamental physics and the standard cosmological model. However, uncertainties still exist in current reaction rates of 7 Li(d,n)2 4 He widely used in big bang nucleosynthesis (BBN) simulations. In this work, we reevaluate the 7 Li(d,n)2 4 He reaction rate using the latest data on the three near-threshold 9 Be excited states from experimental measurements. We present for the first time uncertainties that are directly constrained by experiments. Additionally, we take into account for the first time the contribution from the subthreshold resonance at 16.671 MeV of 9 Be. We obtain a 7 Li(d,n)2 4 He rate that is overall smaller than the previous estimation by about a factor of 60 at the typical temperature of the onset of primordial nucleosynthesis. We implemented our new rate in BBN calculations, and we show that the new rates have a very limited impact on the final light element abundances in uniform density models. Typical abundance variations are in the order of 0.002%. For nonuniform density BBN models, the predicted 7 Li production can be increased by 10% and the primordial production of light nuclides with mass number A > 7 can be increased by about 40%. Our results confirm that the cosmological lithium problem remains a long-standing unresolved puzzle from the standpoint of nuclear physics.

79 ASTRONOMY AND ASTROPHYSICS↗

Parsec-scale Variations in the {sup 7}Li i/{sup 6}Li i Isotope Ratio Toward IC 348 and the Perseus OB 2 Association

Measurements of the lithium isotopic ratio in the diffuse interstellar medium from high-resolution spectra of the Li i λ 6708 resonance doublet have now been reported for a number of lines of sight. The majority of the results for the {sup 7}Li/{sup 6}Li ratio are similar to the solar system ratio of 12.2, but the line of sight toward o Per, a star near the star-forming region IC 348, gave a ratio of about two, the expected value for gas exposed to spallation and fusion reactions driven by cosmic rays. To examine the association of IC 348 with cosmic rays more closely, we measured the lithium isotopic ratio for lines of sight to three stars within a few parsecs of o Per. One star, HD 281159, has {sup 7}Li/{sup 6}Li ≃ 2 confirming production by cosmic rays. The lithium isotopic ratio toward o Per and HD 281159 together with published analyses of the chemistry of interstellar diatomic molecules suggest that the superbubble surrounding IC 348 is the source of the cosmic rays.

79 ASTRONOMY AND ASTROPHYSICS↗

Astrophysical impact of the updated {sup 9}Be(p,α){sup 6}Li and {sup 10}B(p,α){sup 7}Be reaction rates as deduced by THM

The complete understanding of the stellar abundances of lithium, beryllium, and boron represents one of the most interesting open problems in astrophysics. These elements are largely used to probe stellar structure and mixing phenomena in different astrophysical scenarios, such as pre-main-sequence or main-sequence stars. Their different fragility against (p,α) burning reactions allows one to investigate different depths of the stellar interior. Such fusion mechanisms are triggered at temperatures between T ≈ (2–5) × 10{sup 6} K, thus defining a corresponding Gamow energy between ≈ 3–10 keV, where S(E)-factor measurements need to be performed to get reliable reaction rate evaluations. The Trojan Horse Method is a well defined procedure to measure cross sections at Gamow energies overcoming the uncertainties due to low-energy S(E)-factor extrapolation as well as electron screening effects. Taking advantage of the THM measure of the {sup 9}Be(p,α){sup 6}Li and {sup 10}B(p,α){sup 7}Be cross sections, the corresponding reaction rates have been calculated and compared with the evaluations by the NACRE collaboration, widely used in the literature. The impact on surface abundances of the updated {sup 9}Be and {sup 10}B (p,α) burning rates is discussed for pre-MS stars.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Elucidating the Phase Transformation of Li 4 Ti 5 O 12 Lithiation at the Nanoscale

Here this work provides insight regarding the fundamental lithiation and delithiation mechanism of the popular lithium ion battery anode material, Li 4 Ti 5 O 12 (LTO). Our results quantify the extent of reaction between Li 4 Ti 5 O 12 and Li 7 Ti 5 O 12 at the nanoscale, during the first cycle. Lithium titanate’s discharge (lithiation) and charge (delithiation) reactions are notoriously difficult to characterize due to the zero-strain transition occurring between the end members Li 4 Ti 5 O 12 and Li 7 Ti 5 O 12 . Interestingly, however, the latter compound is electronically conductive, while the former is an insulator. We take advantage of this critical property difference by using conductive atomic force microscopy (c-AFM) to locally monitor the phase transition between the two structures at various states of charge. To do so, we perform ex situ characterization on electrochemically cycled LTO thin-films that are never exposed to air. We provide direct confirmation of the manner in which the reaction occurs, which proceeds via percolation channels within single grains. We complement scanning probe analyses with an X-ray photoelectron spectroscopy (XPS) study that identifies and explains changes in the LTO surface structure and composition. Additionally, we provide a computational analysis to describe the unique electronic differences between LTO and its lithiated form.

36 MATERIALS SCIENCE↗

La 2 Zr 2 O 7 Nanoparticle-Mediated Synthesis of Porous Al-Doped Li 7 La 3 Zr 2 O 12 Garnet

In this work, we modified the reaction pathway to quickly (minutes) incorporate lithium and stabilize the ionic conducting garnet phase by decoupling the formation of a La–Zr–O network from the addition of lithium. To do this, we synthesized La 2 Zr 2 O 7 (LZO) nanoparticles to which LiNO 3 was added. This method is a departure from typical solid-state synthesis methods that require high-energy milling to promote mixing and intimate particle–particle contact and from sol–gel syntheses as a unique porous microstructure is obtained. We show that the reaction time is limited by the rate of nitrate decomposition and that this method produces a porous high-Li-ion-conducting cubic phase, within an hour, that may be used as a starting structure for a composite electrolyte.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Battery Relevant Electrochemistry of Ag 7 Fe 3 (P 2 O 7 ) 4 : Contrasting Contributions from the Redox Chemistries of Ag + and Fe 3+

Ag 7 Fe 3 (P 2 O 7 ) 4 is an example of an electrochemical displacement material which contains two different electrochemically active metal cations, where one cation (Ag + ) forms metallic silver nanoparticles external to the crystals of Ag 7 Fe 3 (P 2 O 7 ) 4 via an electrochemical reduction displacement reaction, while the other cation (Fe +3 ) is electrochemically reduced with the retention of iron cations within the anion structural framework concomitant with lithium insertion. These contrasting redox chemistries within one pure cathode material enable high rate capability and reversibility when Ag 7 Fe 3 (P 2 O 7 ) 4 is employed as cathode material in a lithium ion battery (LIB). Further, pyrophosphate materials are thermally and electrically stable, desirable attributes for cathode materials in LIBs. In this article, a bimetallic pyrophosphate material Ag 7 Fe 3 (P 2 O 7 ) 4 is synthesized and confirmed to be a single phase by Rietveld refinement. Electrochemistry of Ag 7 Fe 3 (P 2 O 7 ) 4 is reported for the first time in the context of lithium based batteries using cyclic voltammetry and galvanostatic discharge–charge cycling. The reduction displacement reaction and the lithium (de)insertion processes are investigated using ex situ X-ray absorption spectroscopy and X-ray diffraction of electrochemically reduced and oxidized Ag 7 Fe 3 (P 2 O 7 ) 4 . Ag 7 Fe 3 (P 2 O 7 ) 4 exhibits good reversibility at the iron centers indicated by ~80% capacity retention over 100 cycles following the initial formation cycle and excellent rate capability exhibited by ~70% capacity retention upon a 4-fold increase in current.

25 ENERGY STORAGE↗

Experimental Investigation of Ternary Alloys for Fusion Breeding Blankets

Future fusion power plants based on the deuterium-tritium (DT) fuel cycle will be required to breed the T fuel via neutron reactions with lithium, which will be incorporated in a breeding blanket that surrounds the fusion source. Recent work by LLNL proposed the used of liquid Li as the breeder in an inertial fusion energy (IFE) power plant. Subsequently, an LDRD was initiated to develop alternatives ternary alloy liquid metal breeders that have reduced chemical reactivity with water and air compared to pure Li. Part of the work plan was to experimentally investigate the phase diagrams of ternary alloys. Of particular interest was measurement of the melt temperature, which must be low enough to be compatible with the temperature limits of the steel used in the construction of the chamber and heat transfer system.

36 MATERIALS SCIENCE↗

Neutron production and dosimetry with D(D,n) 3 He, 12 C(D,n) 13 N and 7 Li(p,n) 7 Be reactions at the Sandia Ion Beam Laboratory

Neutrons are produced at the Sandia Ion Beam Laboratory (IBL) using a beam of 280 keV D 2 + ions onto an erbium deuteride target. At test locations in the forward direction these neutrons have energies of about 2.9 MeV and a maximum flux on the flange of the test chamber of about 10 10 n/cm 2 /hour. Dosimetry is done by counting associated charged particles and by nickel foil activation dosimetry. Neutrons with higher energies, up to 6 MeV are produced using higher energy deuterium, up to 3 MeV, from the Pelletron ion accelerator at the IBL on a deuteride target. This report provides detailed information on the methods used for the production and dosimetry of neutrons by the D(D,n) 3 He nuclear reaction at the IBL. Neutron production by the 7 Li(p,n) 7 Be reaction with a proton beam from the Pelletron on a lithium target, such as LiF is also discussed. This produces neutrons with lower energy, in the range from about 0.1 to 1.3 MeV. Neutron production by the 12 C(D,n) 13 N reaction is also discussed. The purpose of this report is to provide information needed to test the effects of neutron irradiation on semiconductor materials and devices at the Sandia IBL.

36 MATERIALS SCIENCE↗

Big-Bang Nucleosynthesis and Primordial Lithium Abundance Problem

Prediction of the primordial abundances of elements in the big-bang nucleosynthesis (BBN) is one of the three strong evidences for the big bang model. Precise knowledge of the baryon-to-photon ratio of the Universe from observations of the anisotropies of cosmic microwave background radiation has made the Standard BBN a parameter-free theory. Although, there is a good agreement over a range of nine orders of magnitude between abundances of light elements deduced from observations and calculated in primordial nucleosynthesis, there remains a yet-unexplained discrepancy of {sup 7}Li abundance higher by a factor of ~3 when calculated theoretically. The primordial abundances depend on the astrophysical nuclear reaction rates and on three additional parameters, the number of light neutrino flavors, the neutron lifetime and the baryon-to-photon ratio in the Universe. The effect of the modification of thirty-five reaction rates on light element abundance yields in BBN was investigated earlier by us. In the present work we have incorporated the most recent values of neutron lifetime and the baryon-to-photon ratio and further modified {sup 3}He({sup 4}He, γ){sup 7}Be reaction rate which is used directly for estimating the formation of {sup 7}Li as a result of β{sup +} decay as well as the reaction rates for t({sup 4}He,γ){sup 7}Li and d({sup 4}He,γ){sup 6}Li. We find that these modifications reduce the theoretically calculated abundance of {sup 7}Li by ~12%.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Experimental and Theoretical Research on the Angular Distribution of Neutrons Produced in {sup 7}Li(p, n){sup 7}Be Reactions during the Interaction of Intense Laser Pulses with Solid Targets

Experiments to measure the angular distribution of neutrons produced in {sup 7}Li(p, n){sup 7}Be nuclear reactions have been carried out at the “Neodymium” picosecond laser facility. A beam of protons was generated on the rear side of a thin aluminum target irradiated by laser radiation with a maximum flux density of 3 × 10{sup 18} W cm{sup –2} (λ = 1.055 μm). Traces of organic compounds on the target surface were the source of protons. Protons were incident on a massive LiF target in which the above nuclear reactions occurred. Our measurements have shown that the neutron flux is anisotropic with a degree of anisotropy equal to 2. We have analyzed the angular distribution of the neutron flux using numerical calculations. We show that at certain proton beam parameters characterizing the energy and angular spectra of protons, it is possible to reproduce the experimentally measured angular distribution of the neutron flux. There are proton beam parameters at which the degree of anisotropy of the neutron flux can be increased several-fold compared to the experimentally measured one.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Thermonuclear Reaction Rates and Primordial Nucleosynthesis

Assuming the best numerical value for the cosmic baryonic density and the existence of three neutrino flavors, standard Big Bang nucleosynthesis is a parameter-free model. It is important to assess if the observed primordial abundances can be reproduced by simulations. Numerous studies have shown that the simulations overpredict the primordial 7 Li abundance by a factor of ≈3 compared to the observations. The discrepancy may be caused by unknown systematics in 7 Li observations, poorly understood depletion of lithium in stars, errors in thermonuclear rates that take part in the lithium and beryllium synthesis, or physics beyond the standard model. Here, we focus on the likelihood of a nuclear physics solution. The status of the key nuclear reaction rates is summarized. Big Bang nucleosynthesis simulations are performed with the most recent reaction rates, and the uncertainties of the predicted abundances are established using a Monte Carlo technique. Correlations between abundances and reaction rates are investigated based on the metric of mutual information. The rates of four reactions impact the primordial 7 Li abundance: 3 He(α,γ) 7 Be, d(p,γ) 3 He, 7 Be(d,p)2α, and 7 Be(n,p) 7 Li. We employ a genetic algorithm to search for simultaneous rate changes in these four reactions that may account for all observed primordial abundances. Furthermore, when the search is performed for reaction rate ranges that are much wider than recently reported uncertainties, no acceptable solutions are found. Based on the currently available evidence, we conclude that it is highly unlikely for the cosmological lithium problem to have a nuclear physics solution.

79 ASTRONOMY AND ASTROPHYSICS↗

Rapid pyrolysis to form super ionic conducting lithium garnets

A method of preparing a lithium-ion conducting garnet via low-temperature solid-state synthesis is disclosed. The lithium-ion conducting garnet comprises a substantially phase pure aluminum-doped cubic lithium lanthanum zirconate (Li 7 La 3 Zr 2 O 14 ). The method includes preparing nanoparticles comprising lanthanum zirconate (La 2 Zr 2 O 7 -np) via pyrolysis-mediated reaction of lanthanum nitrate (La(NO 3 ) 3 ) and zirconium nitrate (Zr(NO 3 ) 4 ). The method also includes pyrolyzing a solid-state mixture comprising the La 2 Zr 2 O 7 -np, lithium nitrate (LiNO 3 ), and aluminum nitrate (Al(NO 3 ) 3 ) to give the Li 7 La 3 Zr 2 O 14 and thereby prepare the lithium-ion conducting garnet. A lithium-ion conducting garnet prepared via the method is also disclosed.

Daemen, Luc L.↗

Learning heterogeneous reaction kinetics from X-ray movies pixel-by-pixel

Reaction rates at spatially heterogeneous, unstable interfaces are notoriously difficult to quantify, yet are essential in engineering many chemical systems, such as batteries 1 and electrocatalysts 2. Experimental characterizations of such materials by operando microscopy produce rich image datasets 3–6, but data-driven methods to learn physics from these images are still lacking because of the complex coupling of reaction kinetics, surface chemistry and phase separation 7. Here we show that heterogeneous reaction kinetics can be learned from in situ scanning transmission X-ray microscopy (STXM) images of carbon-coated lithium iron phosphate (LFP) nanoparticles. Combining a large dataset of STXM images with a thermodynamically consistent electrochemical phase-field model, partial differential equation (PDE)-constrained optimization and uncertainty quantification, we extract the free-energy landscape and reaction kinetics and verify their consistency with theoretical models. We also simultaneously learn the spatial heterogeneity of the reaction rate, which closely matches the carbon-coating thickness profiles obtained through Auger electron microscopy (AEM). Across 180,000 image pixels, the mean discrepancy with the learned model is remarkably small (<7%) and comparable with experimental noise. Our results open the possibility of learning nonequilibrium material properties beyond the reach of traditional experimental methods and offer a new non-destructive technique for characterizing and optimizing heterogeneous reactive surfaces.

Chueh, William↗

Lithium insertion properties of Li{sub x}TiNb{sub 2}O{sub 7} investigated by neutron diffraction and first-principles modelling

TiNb{sub 2}O{sub 7}, a good candidate as anode in lithium batteries, was treated with n-butyllithium to synthesize Li{sub x}TiNb{sub 2}O{sub 7} phases similar to those formed during electrochemical reactions. The Li{sub 2.67}TiNb{sub 2}O{sub 7} and Li{sub 3.33}TiNb{sub 2}O{sub 7} compounds, monoclinic C2/m, were studied by time-of-flight powder neutron diffraction. Their crystal structures, containing 3×3 blocks of (Ti,Nb)O{sub 6} octahedra, were Rietveld refined including Li positions. The Li atoms are distributed in similar amounts over sites with (Li–O) Coordination Numbers 5 and 4, although CN=5 should be preferred for having lower energy. Quantum-mechanical calculations were also performed, determining the average charge–discharge voltages to be 1.415 and 1.571 V for Li{sub 3.33}TiNb{sub 2}O{sub 7} and Li{sub 2.67}TiNb{sub 2}O{sub 7}, respectively, in good agreement with experimental results. An analysis of the theoretical charge distribution shows that, on lithiation, the chemical reduction of Ti and Nb atoms concentrates in the more condensed peripheral octahedra of the 3×3 block. This corresponds to electrons moving into a partly spin-polarized small band which gives rise to semi-metallic conductivity. - Graphical abstract: Structure of monoclinic Li{sub 3.33}TiNb{sub 2}O{sub 7}, and corresponding electron density of states. - Highlights: • Lithium was chemically inserted into the battery anode material TiNb{sub 2}O{sub 7}. • Li atoms are distributed over four- and fivefold oxygen coordinated sites. • On lithiation Nb and Ti atoms are reduced according to a peculiar structural pattern. • Theoretically predicted charge–discharge voltages fit experiments very well.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Investigation of Complex Intermediates in Solvent-Mediated Synthesis of Thiophosphate Solid-State Electrolytes

Lithium thiophosphates represent a promising class of solid Li + conductors for all-solid-state batteries. Scalable solvent-mediated synthesis routes for several Li–P–S ternary compounds have been reported, but little is known regarding the reaction mechanism of such pathways. This work demonstrates that solvent-mediated synthesis of lithium thiophosphate solid electrolytes from mixtures of Li 2 S and P 2 S 5 proceeds through a highly soluble P 2 S 6 2– intermediate. This intermediate exhibits virtually the same Raman spectra in several solvents including acetonitrile, methyl acetate, ethyl acetate, ethyl propionate, dimethoxyethane, tetraethylene glycol dimethyl ether, and tetrahydrofuran. Additionally, based on this universal intermediate, a general reaction mechanism is proposed for the solvent-mediated synthesis of several lithium thiophosphates including (LiPS 3 ) n , Li 2 P 2 S 6 , Li 7 P 3 S 11 , and Li 3 PS 4 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗