Li Nuclei Research Articles

A non-isothermal kinetic study on the extraction of metals from spent lithium iron phosphate batteries using the NH2SO3H roasting process

The non-isothermal kinetics of retired lithium iron phosphate (LiFePO4) battery powder and amino sulfonic acid (NH2SO3H) roasting were studied using TG-DSC. The results show that there are three stages of weight loss: loss of adsorbed water, decomposition and reaction of NH2SO3H (stage Ⅱ), and formation and growth of Li and Fe sulfate nuclei (stage Ⅲ). The apparent activation energy (E) and pre-exponential factor (ln(A)) of NH2SO3H decomposition and reaction were 159.85 kJ/mol and 32.02 S−1, respectively. Similarly, the apparent E and ln(A) formed by Li and Fe sulfate were 113.89 kJ/mol and 11.55 S−1, respectively. Furthermore, the formation of new phases in the second stage reaction is controlled by nucleation and growth. The nucleation and growth of Li and Fe sulfates in the third stage not only occur at this stage, but their rates are also controlled by diffusion. The dynamic equations for the second and third stages are as follows:[−ln(1−α)]13=8.06×1013exp(-1.60×105RT)t[−ln(1−α)]23=1.04×105exp(-1.14×105RT)t

Solid-State Lithium Batteries with In Situ Polymerized Acrylate-Based Electrolytes Capable of Electrochemically Stable Operation at 100 °C.

Solid polymer electrolytes (SPEs) typically consist of salts with mobile anions that could cause instabilities and parasitic side reactions in solid-state lithium (Li) batteries. To address this challenge, single-Li-ion conducting (SLIC) SPEs, where anions of Li salts are covalently attached to the polymer backbone, have been utilized to reduce the number of mobile anions. This approach improves the cationic transference number but is accompanied by a loss of ionic conductivity. In this work, we investigate a synergetic approach of using both a polymerizable SLIC salt and a conventional Li salt in a polymer matrix by in situ polymerization of the poly(propylene glycol) acrylate (PPGA) monomer. The synthesized hybrid SPEs show a high ionic conductivity of up to ∼2 × 10-4 S cm-1 and a relatively high Li-ion transference number of ∼0.4. With a significantly reduced fraction of mobile anions in the combined salt SPE, in situ polymerized SPE cells with a LiFePO4 (LFP) cathode achieve a stable performance for over 100 cycles at temperatures as high as 100 °C, which is unattainable with conventional Li salts or electrolytes. Furthermore, solid-state nuclear magnetic resonance spectra provide additional insights into differences in Li nucleus environments and emphasize a reduction in activation energy for hybrid SPEs due to their more open structure. This study opens the path for the fabrication of high-performance solid polymer Li batteries capable of operating at high temperatures using commercial battery fabrication equipment, as in situ polymerized acrylate-based polymers provide drop-in compatibility with conventional battery production, ease of acrylate polymerization, and inexpensive, facile SPE chemistry. We expect that further tuning of the acrylate-based SPE composition may allow further increases in its conductivity without sacrificing its electrochemical stability or mechanical properties.

The Electro-Excitation Form Factors for Low-Lying States of 7Li Nucleus

The transverse electron scattering form factors have been studied for low –lying excited states of 7Li nucleus. These states are specified by J? T= (0.478MeV), (4.63MeV) and (6.68MeV). The transitions to these states are taking place by both isoscalar and isovector components. These form factors have been analyzed in the framework of the multi-nucleon configuration mixing of harmonic oscillator shell model with size parameter brms=1.74fm. The universal two-body of Cohen-Kurath is used to generate the 1p-shell wave functions. The core polarization effects are included in the calculations through effective g-factors and resolved many discrepancies with experiments. A higher configuration effect outside the 1p-shell model space, such as the 2p-shell, enhances the form factors for q-values and reproduces the data. The present results are compared with other theoretical models. PACS: 25.30.Bf Elastic electron scattering - 25.30.Dh Inelastic electron scattering to specific states – 21.60.Cs Shell model – 27.20. +n 5? A ?19

Effect of lithium concentration on the network connectivity of nuclear waste glasses

Structure of borosilicate glasses with varying Li2O contents were investigated using Magic Angle Spinning (MAS) Nuclear Magnetic Resonance (NMR), employing 6Li, 11B, 23Na, 27Al and 29Si nuclei. 11B MAS NMR revealed that increasing Li2O contents result in formation of [BO4]− sites at the expense of BO3. 11B{6Li} and 27Al{6Li} dipolar heteronuclear multiple quantum correlation (D-HMQC) NMR revealed Li as a charge compensator for anionic tetrahedral sites with increased Li. 11B{6Li} J-coupling mediated HMQC NMR suggested the possible association of Li with non-bridging oxygens on Q2 and Q3 sites, indicating its dual role in the glass network. 29Si and 23Na MAS NMR spectra showed depolymerisation of the silicate network and shortening of Na-O bond lengths with increased Li. NMR results are supported by Raman spectroscopy and thermal analysis that indicate depolymerisation of the silicate network and a reduction in glass transition temperature at higher Li content.

Solid-State Lithium Batteries with in-Situ Polymerized Acrylate-Based Electrolytes Capable of Electrochemically Stable Operation at 100 ℃

In-situ polymerized acrylate-based polymers are very appealing as solid polymer electrolytes (SPEs) in lithium (Li) batteries due to the drop-in compatibility of such in-situ polymerization with conventional battery production, the ease of acrylate polymerization and their inexpensive, facile SPE chemistry. We identified, however, that such SPEs suffer from either a low cationic transference number with dual ion conducting salts (0.12-0.2) or a low ionic conductivity with single Li-ion conducting (SLIC) salts (6·10-6 S cm-1). In this project we overcame these limitations and developed significantly improved SPE with ionic conductivity of up to 2·10-4 Scm-1 and a relatively high Li-ion transference number of 0.4. With a significantly reduced fraction of mobile anions in the hybrid SPE, in-situ polymerized SPE cells with an LiFePO4 (LFP) cathode achieve a stable performance for over 100 cycles at temperatures as high as 100 °C, which is unattainable with conventional Li salts or electrolytes. Furthermore, the motional narrowing observed in the line-shapes of solid-state nuclear magnetic resonance (SS-NMR) spectra provided additional insights of the differences in Li nucleus environments and revealed a reduced activation energy for the hybrid salt SPEs due to their more open structure. This study opens the path for the fabrication of high-performance solid polymer lithium batteries capable of operating at high temperatures using commercial battery fabrication equipment. We expect that further tuning of the acrylate based SPE composition may allow further increases in its conductivity without sacrifices in its electrochemical stability or mechanical properties.

Ultrasound Combination to Improve the Efficacy of Current Boron Neutron Capture Therapy for Head and Neck Cancer.

Boron neutron capture therapy (BNCT) is radiotherapy in which a nuclear reaction between boron-10 (10B) in tumor cells and neutrons produces alpha particles and recoiling 7Li nuclei with an extremely short range, leading to the destruction of the tumor cells. Although the neutron source has traditionally been a nuclear reactor, accelerators to generate neutron beams have been developed and commercialized. Therefore, this treatment will become more widespread. Recurrent head and neck cancer (HNC) close to the body surface is considered a candidate for BNCT using the boron compound boronophenylalanine (BPA) and has been found to be highly responsive to this treatment. However, some cases recur early after the completion of the treatment, which needs to be addressed. Ultrasound is a highly safe diagnostic method. Ultrasound with microbubbles is expected to promote the uptake of BPA into tumor cells. Ultrasound also has the ability to improve the sensitivity of tumor cells to radiotherapy. In addition, high-intensity focused ultrasound may improve the efficacy of BNCT via its thermal and mechanical effects. This review is not systematic but outlines the current status of BPA-based BNCT and proposes plans to reduce the recurrence rate of HNC after BNCT in combination with ultrasound.

Machine Learning in the Problem of Extrapolating Variational Calculations in Nuclear Physics

A modified machine learning method is proposed, utilizing an ensemble of artificial neural networks for the extrapolation of energies obtained in variational calculations, specifically in the No-core Shell Model (NCSM), to the case of the infinite basis. A new neural network topology is employed, and criteria for selecting both the data used for training and the trained neural networks for statistical analysis of the results are formulated. The approach is tested by extrapolating the deutron ground state energy in calculations with the Nijmegen II NN interaction and provides statistically significant results. This technique is applied to obtain extrapolated ground state energies of 6Li and 6He nuclei based on the NCSM calculations with Daejeon16 NN interaction.

Hyperfine interactions of paramagnetic radiation-induced defect centres in advanced ceramic breeder pebbles

Advanced ceramic breeder (ACB) pebbles consisting of 65 mol% lithium orthosilicate (Li4SiO4) and 35 mol% lithium metatitanate (Li2TiO3) are developed for tritium breeding in the European Union’s (EU) helium cooled pebble bed (HCPB) breeder blanket concept of the demonstration fusion power plant (DEMO). Electron-nuclear double resonance (ENDOR) spectroscopy is a powerful and widely used magnetic resonance technique that combines aspects of electron paramagnetic resonance (EPR) and nuclear magnetic resonance (NMR). In the present work, ENDOR spectroscopy was applied to investigate hyperfine (HF) interactions of paramagnetic radiation-induced defect centres (containing unpaired electrons) in the biphasic ACB pebbles after irradiation with 10 MeV accelerated electrons. To separate individual EPR signals of the formed and accumulated paramagnetic centres, isochronal annealing of the irradiated ACB pebbles followed by EPR spectra measurements at X- and Q-microwave frequency bands at room and low temperature were performed. Afterwards, X-band ENDOR spectra at low temperature were recorded for selected EPR signals to reveal HF interactions between the unpaired electron spins with the spins of magnetic 7Li and 1H isotope nuclei. The g-factor and HF coupling values determined from EPR and ENDOR spectra simulations provide novel insights into the local structure of paramagnetic hole- and electron-type centres in the irradiated ACB pebbles.

Ultrauniform Plating of Lithium on 10-nm-Scale Ordered Carbon Grids for Long Lifespan Lithium Metal Batteries.

Tailorable lithium (Li) nucleation and uniform early-stage plating is essential for long-lifespan Li metal batteries. Among factors influencing the early plating of Li anode, the substrate is critical, but a fine control of the substrate structure on a scale of ≈10nm has been rarely achieved. Herein, a carbon consisting of ordered grids is prepared, as a model to investigate the effect of substrate structure on the Li nucleation. In contrast to the individual spherical Li nuclei formed on the flat graphene, an ultrauniform and nuclei-free Li plating is obtained on the ordered carbon with a grid size smaller than the thermodynamical critical radius of Li nucleation (≈26nm). Simultaneously, an inorganic-rich solid-electrolyte-interphase is promoted by the cross-sectional carbon layers of such ordered grids which are exposed to the electrolyte. Consequently, the carbon grids with a grid size of ≈10nm show a favorable cycling stability for more than 1100 cycles measured at 2mA cm-2 in a half cell. With LiNi0.8Co0.1Mn0.1O2 as cathode, the assembled full cell with a cathode capacity of 3 mAh cm-2 and a negative/positive ratio of 1.67 demonstrates a stable cycling for over 130 cycles with a capacity retention of 88%.

A parallel line probe for spatially selective electrochemical NMR spectroscopy

In situ NMR is a valuable tool for studying electrochemical devices, including redox flow batteries and electrocatalytic reactors, capable of detecting reaction intermediates, metastable states, time evolution of processes or monitoring stability as a function of electrochemical conditions. Here we report a parallel line detector for spatially selective in situ electrochemical NMR spectroscopy. The detector consists of 17 copper wires and is doubly tuned to 1H/19F and X nuclei ranging from 63Cu (106.1 MHz) to 7Li (155.5 MHz). The flat geometry of the parallel line detector allows its insertion into a high electrode surface-to-volume electrochemical flow reactor, enabling a detector-in-a-reactor design. This integrated device is named “eReactor NMR probe”. Combined with B1-selective pulse sequences, selective detection of the nuclei at the electrode-electrolyte interface, that is within a distance of 800 μm from the electrode surface, has been achieved. The selective detection of 7Li and 19F nuclei is demonstrated using two electrolytes, LiCl and LiBF4 solutions, respectively. A good B1 homogeneity with an 810° to 90° pulse intensity ratio of 68–72 % was achieved. Using electrochemical plating of lithium metal as a model reaction, we further demonstrated the operando functionality of the probe. The new eReactor NMR probe offers a general method for studying flow electrochemistry, and we envision applications in a wide range of environmentally relevant energy systems, for example, Li metal batteries, electrochemical ammonia synthesis, carbon dioxide capture and reduction, redox flow batteries, fuel cells, water desalination, lignin oxidation etc.

Operando Optical Microscopy of Dead Lithium Growth in Anode‐Less Configuration

AbstractThere is an increasing demand to improve battery safety and performance as part of the global push to convert the small electronics and transportation sector to infrastructures based on electricity. This work follows the deposition of lithium metal in anode‐less conditions by an operando optical microscope using a transparent indium tin oxide‐polyethylene terephthalate (ITO‐PET) window as the current collector in a readily‐available electrochemical set‐up. The mechanism of Li metal nucleation strongly depends on the selected current densities (C/40 and 2C). After the deposition of the solid electrolyte interface (SEI), Li nucleates from mossy to needle morphology. Moreover, layer‐by‐layer growth of dead Li in voids is monitored by following its accumulation upon cycling. Dead Li deposits in residual hollow structures, especially when high current densities are applied. These optical observations are coupled with computer vision analyses to evaluate the average size of the Li deposits: smaller Li nuclei plate when high C‐rate is applied. The results here described provide insights into a new electrochemical cell concept that enables to elucidate the influence of spatial inhomogeneities of the lithophilic ITO‐PET surface on the mechanism of Li nucleation and plating.

Comparative study for the elastic scattering of the isobar nuclei 6Li and 6He on 64Zn using different nuclear potentials

The available experimental data for the elastic scattering of the isobar nuclei 6Li and 6He on [Formula: see text]Zn have been reanalyzed in the available energy range using the optical model, double folding (DF) (Sao Paulo), and crystal model (CM). Double-folding (DF) and crystal model (CM) have been used to investigate the experimental data as a real part of the optical potential, while the imaginary part was taken in Woods–Saxon (WS) shape. One value of the real part of the optical potential has been applied to the two systems under consideration. The distance of the closest approach of the 6Li (6He) + [Formula: see text]Zn systems has been extracted from the available experimental data using different methods. The extracted potential from the 6Li and 6He elastically scattered by [Formula: see text]Zn data could be used as the basis for the creation of a simple global optical potential for 6Li and 6He. The extracted normalization factor ([Formula: see text]) was equal to the unity during the fitting process avoiding its unfortunate value (in the range 0.5–0.7) exists in the literature. It was observed that interaction distances vary slowly with the energy of the projectile and strongly depend on the projectile properties. The halo properties of 6He have a significant effect on the calculated reaction cross-sections. Different methods have been applied to 6He and 6Li elastically scattered by [Formula: see text]Zn, where fair agreement between them has been observed.

Regulating Lithium Nucleation at the Electrolyte/Electrode Interface in Lithium Metal Batteries

AbstractLithium (Li) metal has emerged as a viable alternative anode material to address the current energy density shortfalls in Li batteries. However, its integration into widespread implementation remains somewhat constrained due to the substandard reversibility issues and safety concerns arising from erratic Li deposition. To effectively tackle these obstacles, considerable endeavors have been exerted to modulate the morphology of Li deposition. Nevertheless, it is exceedingly challenging for Li nuclei that tend to dendritic growth thermodynamically to transform into dense Li morphologies during their growth process. Therefore, it is crucial to understand what influences the formation process of Li nuclei and how to improve the state of Li nuclei. Herein, Li nucleation mechanisms involving mass transport across the solid electrolyte interface from electrolyte to electrode and electrode interfacial reactions are elucidated. Inspired by the understanding of Li nucleation, the corresponding design principles, including enhancing and homogenizing mass transport, stabilizing solid electrolyte interface film, and regulating surface interaction/selection, are summarized for optimizing Li nucleation and further inducing dendrite‐free Li deposition. In light of the competition among these design principles, a perspective on the existing challenges and opportunities for further promoting the application of Li metal batteries is proposed.

Detailed analysis of the 6Li breakup in the field of the 209Bi nucleus

Abstract At energies between 24 and 50 MeV, the angular distributions of 6Li + 209Bi elastic scattering are reanalyzed phenomenologically as well as microscopically. The performed analysis adds to previous studies and aims to further explore the cluster nature of the 6Li nucleus by examining the associated breakup effects on the elastic scattering channel, in addition to probing the consistency of the different implemented potentials in reproducing the considered data. The strong coupling to the breakup channel has a strong influence on elastic data and reproduces a repulsive dynamical polarization potential (DPP), which dramatically reduces the real potential strengths. Such an observed effect was simulated by introducing a semi-microscopic repulsive DPP as well as by applying the continuum discretized coupled channels (CDCC) method. The analysis was extended to check the effect of direct deuteron stripping 209Bi(6Li,d)211Po on the elastic 6Li + 209Bi channel.

Peptide Conjugated Boron Neutron Capture Therapy for Enhanced Tumor Targeting.

A cutting-edge non-invasive cancer treatment method called boron neutron capture therapy (BNCT) allows for the removal of cancerous tumor cells with the least possible damage to healthy tissue. It involves the exposure of cancer cells with low-energy thermal neutrons, boron-10 (10B) cellular uptake causes cancer cell death by producing alpha particles and recoiling lithium-7 (7 Li) nuclei. Despite positive outcomes from clinical trials conducted all around the world, these substances have relatively limited tumor selectivity or low boron content per molecule. The development of new boron delivery agents with more selectivity and enhanced boron loading would advance this technique and promote its use in clinics as a primary cancer treatment. As peptide-binding cell surface receptors are typically overexpressed on cancer cells, they can be seen as interesting targets for targeted tumor therapy. The attachment of meta-carboranes to peptide conjugates that target tumor cells specifically by their overexpressed receptors may be a method to get around these problems. A state-of-the-art overview of current developments in the application of BNCT for cancer targeted therapy via peptide conjugation is the goal of this review.

NMR detection of the strained metallacycles in organolithiums: theoretical study.

For the first time through quantum chemistry methods, the effective use of 1JCLi spin-spin coupling constants as descriptors for assessing the formation of strained metallacycles is demonstrated. Both acyclic organolithiums and 3- to 7-membered metallacycles are examined. 80 organolithium compounds, including both monomeric and dimeric species, with ligands containing fluorine, nitrogen, oxygen, and carbon (in the form of carbanions), are tested. In general, the 1JCLi values below 12 Hz for monomeric species and below 6 Hz for dimeric species serve as clear indicators of strained monomeric metallacycle formation (for 6Li nuclei). The primary contributor to the overall 1JCLi value is the Fermi-contact term, which correlates directly with the carbon-lithium interatomic distance and allows to distinguish between dimers and monomers.

Asymptotic normalization coefficient for the study of the mirror nuclei 7Li and 7Be

We present a theoretical study of the nuclear structure of the mirror nuclei 7Li and 7Be by using the asymptotic normalization coefficient (ANC) method through the transfer reactions 6Li(d,p)7Li and 6Li(3He,d)7Be. For these reactions, the elastic scattering and the transfer angular distributions were calculated considering cluster structures for the residual nucleus and the transfer particle. With the use of the Fresco code, we found the optical model parameters which reproduce the experimental data for the elastic and the transfer angular distributions and we got the ANC for the single particle model and the spectroscopic factor on the ground and the first excited states of each nuclei. This methodology allows to calculate the nuclear ANC which describes the peripheral behavior of both nuclei on their bound states.

Electrodeposited Lithiophilic Zn Thin Film on the Current Collector for Improved Cyclability of Anode-Free Lithium Metal Battery

Anode-free lithium metal batteries (AFMBs) are recently presented as the new generation of Li metal batteries benefiting high gravimetric and volumetric energy densities due to the zero excess lithium. However, poor electrochemical stability and maximum cyclability of around 40-50 cycles due to the zero excess Lithium prevent the AFLMBs to be functional1. Here, lithiophilic electrodeposited Zn thin film on the current collector is reported in order to decrease the lithium nucleation overpotential and improve the plating/stripping process during alloying and dealloying. Moreover, columbic efficiency is increased by applying more zinc coated on the cupper current collector and by providing a more hospitable site for Li nuclei to plate2. Due to the alloy formation of Li-Zn, more conformal Li growth on the current collector is provided and homogeneous Li distribution and smooth morphology are observed by SEM images. The cells in different zinc thin layer coating are cycled with different current densities as well as long-term cycling by galvanostatic cycling charge-discharge cycling. As a result, increasing the thin film thickness up to 1 micron significantly enhances the electrochemical stability of the cells such as higher columbic efficiency and cyclability, lower Li nucleation overpotential. Finally, the Li-ion chemical diffusion coefficients DLi, are evaluated by galvanostatic intermittent titration technique (GITT) and electrochemical impedance spectroscopy (EIS) and the results are compared to each other3.References Maddukuri, S. et al. On the challenge of large energy storage by electrochemical devices. Electrochim Acta 354, 136771 (2020).Merso, S. K. et al. An in-situ formed bifunctional layer for suppressing Li dendrite growth and stabilizing the solid electrolyte interphase layer of anode free lithium metal batteries. J Energy Storage 56, 105955 (2022).Xie, J. et al. Determination of Li-ion diffusion coefficient in amorphous Zn and ZnO thin films prepared by radio frequency magnetron sputtering. Thin Solid Films 519, 3373–3377 (2011).

Optical-Model Analysis of the Elastic Scattering of Protons on a 7Li Nucleus, Including the Resonant Contribution

Optical-Model Analysis of the Elastic Scattering of Protons on a 7Li Nucleus, Including the Resonant Contribution

Refinement of the Optical Potential Parameters of the Elastic Scattering of Protons on a 6Li Nucleus

Refinement of the Optical Potential Parameters of the Elastic Scattering of Protons on a 6Li Nucleus