Li Crystals Research Articles

Enhancement of alpha/beta ratio in NaI:Tl,6Li neutron-gamma scintillators by rare earth co-doping

NaI:Tl,6Li bulk crystals are regarded as promising neutron-gamma (n-γ) scintillators because of low production cost and superior n-γ pulse shape discrimination (PSD) performance. In this work, some rare earth elements (Gd, Y, Lu and Sc) co-doped NaI:Tl,6Li single crystals were grown by the multi-ampoule Bridgman method. It was found that the rare earth co-doping significantly improves the pulse height discrimination (PHD) capability of NaI:Tl,6Li with high alpha/beta (α/β) ratio, approaching to 100%. The optimal α/β ratios achieved for Gd, Y, Lu and Sc co-doped NaI:Tl,6Li are 0.85, 0.93, 0.95, and 0.83, respectively. Electron equivalent energy per neutron interaction is above 3.96 MeV and can be as high as 4.54 MeV, close to the Q value of 4.78 MeV for 6Li(n, α)3H interaction. Moreover, the rare earth co-doped NaI:Tl,6Li crystals still maintain the superior PSD capability with figure of merit (FoM) in the range of 2.1–3.3. These results highlight the great potential of rare-earth co-doped NaI:Tl,6Li crystals serving as high-performance n-γ scintillators.

Growth Process and Optical Properties of Cs2ZrCl6 Doped with Ce3+ and Li+ Crystals

Cs2ZrCl6 (CZC) has very promising scintillation properties in the application of gamma-ray spectroscopy. So far, undoped crystals of this composition have been studied, but the growth of the large-scale doped single crystals has not been reported so far. In this paper, a process improvement strategy is reported. Large-scale Cs2ZrCl6:Ce,Li (CZC:Ce,Li) single crystals with excellent energy resolution are obtained by appropriately adjusting the temperature gradient and growth rate. CZC:Ce,Li single crystals doped with 0.5, 1.5, and 3.0 mol % Ce3+ were grown by the Bridgman method. After the phase purity of the sample was determined by X-ray diffraction analysis, the crystal defects were determined by the energy-dispersive X-ray spectroscopy, and the crystal growth process was improved on this basis. The transmission spectrum confirmed the improvement of crystal quality. The energy resolution of CZC:Ce,Li crystals grown by the improved process is 4.3%, which confirmed that the improved process is conducive to the growth of bulk doped CZC single crystals, and hence, our results provide a basis for the growth of large-scale doped CZC single crystals.

Quasi-2D FCC lithium crystals inside defective bi-layer graphene: insights from first-principles calculations

Quasi-2D crystals inside bi-layer graphene have been observed in in-situ TEM experiments [Nature 564 (2018) 234]. It was also revealed that Li crystals have the FCC structure, nucleate at point defects in graphene and contain impurity atoms. Using first-principles calculations, we systematically study the interaction of isolated Li atoms and those assembled in FCC crystals with vacancy-type defects in graphene and show that quasi-2D Li crystals encapsulated between graphene sheets must indeed nucleate at the defects and that the interaction of not only isolated Li atoms, but also Li crystals with the defects in graphene is strong. We further demonstrate that a moiré pattern develops at the graphene/Li interface. Finally, we investigate the behavior of impurities most likely to be found in the encapsulated Li crystals, such as O, N, S and F and show that all impurity atoms take octahedral interstitial positions and strongly interact with atoms in Li crystals, thus impeding the de-lithiation process. Our theoretical work focused on the fundamental aspects of the behavior of Li inside bi-layer graphene should help rationalize the results of in-situ TEM experiments and shed light on the role of impurities in the degradation of anode materials during Li-ion battery operation.

Metastable Decomposition Realizing Dendrite‐Free Solid‐State Li Metal Batteries

AbstractA stable interface and preventing dendrite‐growth are two crucial factors to realize long‐life all‐solid‐state Li batteries (ASSLBs) using sulfide‐based solid electrolytes (SEs) and Li metal anodes. But it remains a challenge to accomplish the two factors simultaneously. Here, an effective strategy is reported to realize this goal in Li‐argyrodites via self‐engineered metastable decomposition that is enabled by Si doping in Cl‐rich argyrodites. It is shown that Cl atoms in the lattice become metastable and are highly reactive with Li atoms. The locally deposited/grown Li crystal nuclei are thus depleted by the metastable Cl during electrochemical cycling, in situ generating electrically insulated LiCl shells concentrated at the argyrodite grain boundaries. The shells in turn prevent the autochthonous Li redeposition and act as self‐protective layers to restrain the continuous decomposition in the interior argyrodite, that is, self‐assembly of reactive‐cores‐stable‐shells to Li metal, thereby enabling an ultra‐long life ASSLB using Li metal anodes at room temperature under relatively high current densities.

EFFECT OF DIFFERENT SOLVENTS ON THE OPTICALLY STIMULATED LUMINESCENCE SIGNAL FROM MGB4O7:CE,LI-LOADED POLYMER FILMS.

The detailed dose analysis at the extremities remains a challenge, without affecting operators' mobility and their tactile sense. Using films loaded with optically stimulated luminescence (OSL) crystals have been studied in order to overcome some of these challenges in 2D dosimetry. In this work, we investigated flexible polymeric films loaded with MgB4O7:Ce,Li to acquire a better understanding of the dependence of the dosimetric signal characteristics on the production process and the influence of using different powder grain sizes. In film production, five different solvents were used: acetone-benzene, dichloromethane, chloroform, tetrahydrofuran and formic acid. Our results indicate that acetone-benzene is the solvent mixture that less influences the signal emitted by treated crystals, in comparison with the signal emitted by the pristine crystal powder. Conversely, by using formic acid, the crystalline structure of the sample was most severely modified, leading to a drastic reduction of the emitted OSL signal. We found that the extent of the grain surface in contact with the solvent in the process is important and should be taken into consideration when choosing the proper grain size to be used. Highlights Polymeric films loaded with MgB4O7:Ce,Li crystals were produced using different solvents.Different effect on the OSL signal was found depending on the used solvent.Among the evaluated solvents, acetone-benzene was the one that less affected the OSL signal.

Effect of Li+ co-doping on the luminescence and defects creation processes in Gd3(Ga,Al)5O12:Ce scintillation crystals

Photo- and thermally stimulated luminescence characteristics, as well as photostimulated defects creation processes are investigated in the 85–510 K temperature range for the Li+ co-doped single crystal of Gd3(Ga,Al)5O12:Ce (GAGG:Ce). The results for GAGG:Ce,Li are compared with the corresponding characteristics of the GAGG:Ce and GAGG:Ce, Mg single crystals of similar host composition. The influence of Li+ and Mg2+ ions on the Ce3+ - related emission band position, temperature dependence of the photoluminescence intensity, efficiency of the Gd3+ → Ce3+ energy transfer, intensity and decay kinetics of the afterglow, and thermally stimulated luminescence characteristics is revealed. The presence of the Ce3+ → Ce4+ conversion in GAGG:Ce,Li is confirmed. The conclusion is made that, unlike GAGG:Ce,Mg, the compensation of the Li+ excess negative charge in GAGG:Ce,Li occurs due to both the Ce3+ → Ce4+ conversion and the effective formation of intrinsic crystal lattice defects. The origin of these defects as well as the origin of the electron and hole trapping centers in the GAGG:Ce,Li crystal are discussed.

Radiation defects in NaCl matrix with reduced lattice symmetry caused by light cation doping and elastic uniaxial deformation

The processes of radiation defect creation and radiative relaxation of electronic excitations under applied local or/and uniaxial elastic deformation have been studied in NaCl crystals by means of optical absorption, luminescence and thermoactivation spectroscopy methods. In NaCl:Li at 80 K, X-ray-induced absorption bands peaked around 3.35 and 4.6 eV have been detected and ascribed to interstitial halide atoms located nearby Li impurity cations, HA(Li) centres. Subsequent thermal annealing of HA(Li) centres leads to the formation of polyhalide centres responsible for the absorption band at 5.35 eV. In an X-irradiated and stressed NaCl:Li crystal (degree of uniaxial elastic deformation of ε = 0.9%), the peak of thermally stimulated luminescence at ~115 K is composed of the ~2.7-eV emission appearing, in our opinion, due to the recombination of the electron, thermally released from an F′ centre, with a hole-type HA(Li) centre. The applied uniaxial elastic stress facilitates the self-trapping of anion excitons in regular regions of a NaCl lattice and impedes the energy transfer by mobile excitons to impurities/defects and, in turn, attenuates the Br-related luminescence peaked at 3.95 eV with respect to the π-emission of self-trapped excitons (~3.35 eV). The 3.95 eV emission has been detected in a natural NaCl crystal containing homologous Br impurity ions.

Driving Force of Molecular/Ionic Superfluid Formation

Driving Force of Molecular/Ionic Superfluid Formation

Growth and optical caracteristics of the CsI:Li scintillator crystal for use as radiation detector

Materials capable of converting ionizing radiation into light photons are called scintillators, some have specific efficiencies for certain applications and types of radiation, e.g. gamma, X-ray, alpha, beta and neutrons. CsI:Tl and NaI:Tl crystals are commonly found in the market because they have several applications, but few studies have been done on lithium doped cesium iodide crystal (CsI:Li). The lithium element, in this crystal used as a dopant, is also exploited as a converter for neutron detection, as it has a shock section of 940 barns for thermal neutrons. The study of the CsI:Li crystal is convenient considering the natural abundance of the lithium element with 7.5%, besides the interest in having a low cost national scintillator material with an opportunity to search the response of a detector for different types of radiation. The CsI:Li crystal was grown with molar concentration 10-4 to 10-1, using the vertical Bridgman technique. The parameters involved in the growth process were investigated. The transmittance was evaluated in the spectral region from 190 nm to 1100 nm. Luminescence emission spectra for the CsI:Li crystal were evaluated by photometric analysis of the crystal stimulated with a 137Cs (662 keV) source in front of the coupled sample at the monochromator input. The crystals showed of maximum luminescence intensity at the wavelength of 420 nm. The response of the scintillators when excited with gamma radiation of 241Am, 133Ba, 22Na, 137Cs, 60Co and neutron radiation from the AmBe source, with energy range of 1 MeV to 12 Mev was evaluated.

Reduced-Graphene-Oxide-Guided Directional Growth of Planar Lithium Layers.

Rechargeable lithium (Li) metal batteries hold great promise for revolutionizing current energy-storage technologies. However, the uncontrollable growth of lithium dendrites impedes the service of Li anodes in high energy and safety batteries. There are numerous studies on Li anodes, yet little attention has been paid to the intrinsic electrocrystallization characteristics of Li metal and their underlying mechanisms. Herein, a guided growth of planar Li layers, instead of random Li dendrites, is achieved on self-assembled reduced graphene oxide (rGO). In situ optical observation is performed to monitor the morphology evolution of such a planar Li layer. Moreover, the underlying mechanism during electrodeposition/stripping is revealed using ab initio molecular dynamics simulations. The combined experiment and simulation results show that when Li atoms are deposited on rGO, each layer of Li atoms grows along (110) crystallographic plane of the Li crystals because of the fine in-plane lattice matching between Li and the rGO substrate, resulting in planar Li deposition. With this specific topographic characteristic, a highly flexible lithium-sulfur (Li-S) full cell with rGO-guided planar Li layers as the anode exhibits stable cycling performance and high specific energy and power densities. This work enriches the fundamental understanding of Li electrocrystallization without dendrites and provides guidance for practical applications.

Interstitial Li+ Controls the UV Transmission and the Radiation Hardness in YAG

Optical absorption spectra measured in as‐grown and gamma‐ray irradiated un‐doped YAG, Li‐doped YAG, and Ca‐doped YAG single crystals are compared for characterization of effects introduced by impurities. The studies are conducted on single crystals grown by the vertical Bridgman method. Basing on the Li+ incorporation mechanism, clarification is done regarding the optimal amounts of Li+ for preparation of YAG:Li crystals with low concentration of anion vacancies and related defects giving rise to absorption in the UV range. Differences in behavior are recorded in variously doped crystals subjected to gamma‐ray irradiation; in comparison to un‐doped YAG, the induced absorption coefficient in Li‐doped YAG of optimal composition is lower more than six times. High transmission in the UV and high radiation tolerance are important for most applications of YAG, especially when operated in high radiation fields.

Surface Layer Effects Synergism with Electrolytes for Li Nucleation and Growth

Li metal has been considered the “holy grail” anode materials. Li metal has the most negative potential with an extremely high theoretical specific capacity of 3860 mA h g−1.[1] It is, however, plagued with multiple challenges which need solutions before the realization of this material. Li metal has two main failure mechanisms, one is the random growth of detrimental dendrites, which can lead to rapid thermal runoff, i.e. Galaxy Note 7.[2] The other issue that arises upon cycling is pulverization of lithium metal through none uniform plating, leading to an increase in solid electrolyte formation(SEI) and thereby the increase in voltage polarization within the cell.[3] Both Li failure mechanisms are rooted in the uneven distribution of SEI layers whose properties vary depending on the location of SEI formed.[4] The initial surface chemistry on Li metal influences SEI formation in the very beginning. In this work, electrochemical deposition of Li metal on different substrates with bare oxides has been performed to understand the nucleation and growth of Li crystals. Electrolyte and surface modification give rise to differing SEI properties/composition which leads to improved Li deposition morphology. The fundamental mechanisms that dictates the smooth Li deposition will be discussed.

Enhanced cycling stability of Li–O2 batteries by using a polyurethane/SiO2/glass fiber nanocomposite separator

The cycle performance of Li–O2 batteries is significantly enhanced by using a PU/SiO2/GF nanocomposite separator, which effectively protects the Li anode from corrosion by soluble oxidative intermediates from the ORR, and the dendritic growth of Li crystals during cycling is also inhibited.

Synergistic Effects from Substrate and Electrolytes on Li Deposition

Li metal has been considered the “holy grail” anode materials. Li metal has the most negative potential with an extremely high theoretical specific capacity of 3860 mA h g−1.[1] It is, however, plagued with multiple challenges which need solutions before the realization of this material. Li metal has two main failure mechanisms, one is the random growth of detrimental dendrites, which can lead to rapid thermal runoff, i.e. Galaxy Note 7.[2] The other issue that arises upon cycling is pulverization of lithium metal through none uniform plating, leading to an increase in solid electrolyte formation(SEI) and thereby the increase in voltage polarization within the cell.[3] Both Li failure mechanisms are rooted in the uneven distribution of SEI layers whose properties vary depending on the location of SEI formed.[4] The initial surface chemistry on Li metal influences SEI formation in the very beginning. In this work, electrochemical deposition of Li metal on specific substrate has been performed to understand the nucleation and growth of Li crystals. Electrolyte and substrate have been identified to have synergistic effects on the morphology and efficiency of deposited Li. The fundamental mechanisms that dictates the smooth Li deposition will be discussed.

Highly efficient electroluminescence in sapphire and magnesia

Electroluminescence (EL) has been obtained and studied in two different wide band gap oxide crystals: MgO:Li (7.8eV) and Al2O3:Mg (8.8eV). EL requires crystal doping with Li or Mg to induce p-type conductivity and the formation of F-type centers which are the deep levels within the band gap for electron–hole recombination. Oxidizing treatments are required in Al2O3:Mg to reach adequate conductivities. The main EL emissions are at 2.35eV (528nm) for MgO:Li crystals and at 3.8eV (327nm) for Al2O3:Mg. Trace impurities also produce EL in the visible region, their control may be used for color designed LEDs.

Acoustic waves and phonon focus in Li crystal: the first principle study

Natural Science Foundation of the Education Department of Henan province of China [2009B590001]; Henan Science and Technology Agency of china [092102210314, 132102210207, 14B140010]; Open Project of State Key Laboratory of Superhard Materials (Jilin University) [201107]; National Natural Science Foundation of China [11104127]; Program for Innovative Research in University of Henan Province [13IRTSTHN020]

Face-Centered-Cubic Lithium Crystals Formed in Mesopores of Carbon Nanofiber Electrodes

In the foreseeable future, there will be a sharp increase in the demand for flexible Li-ion batteries. One of the most important components of such batteries will be a freestanding electrode, because the traditional electrodes are easily damaged by repeated deformations. The mechanical sustainability of carbon-based freestanding electrodes subjected to repeated electrochemical reactions with Li ions is investigated via nanotensile tests of individual hollow carbon nanofibers (HCNFs). Surprisingly, the mechanical properties of such electrodes are improved by repeated electrochemical reactions with Li ions, which is contrary to the conventional wisdom that the mechanical sustainability of carbon-based electrodes should be degraded by repeated electrochemical reactions. Microscopic studies reveal a reinforcing mechanism behind this improvement, namely, that inserted Li ions form irreversible face-centered-cubic (FCC) crystals within HCNF cavities, which can reinforce the carbonaceous matrix as strong second-phase particles. These FCC Li crystals formed within the carbon matrix create tremendous potential for HCNFs as freestanding electrodes for flexible batteries, but they also contribute to the irreversible (and thus low) capacity of HCNFs.

Effect of high-energy electron irradiation on forsterite laser crystals

The effect of 21-MeV electron irradiation on the optical absorption characteristics of Czochralski-grown forsterite (Mg2SiO4) single crystals (both undoped and chromium-doped) has been investigated. The irradiation is found to induce additional optical absorption (AOA) in the crystals in the range of 225–1200 nm due to the formation of color centers based on intrinsic host point defects and the change in the oxidation state of chromium ions. The AOA spectra have been decomposed into elementary bands. The influence of the chromium concentration in crystals, the oxygen content in the growth atmosphere, and additional doping with lithium on the behavior of these bands has been analyzed. A possible structure of the color centers responsible for the AOA is discussed. It is shown that the electron irradiation somewhat decreases the intensity of the characteristic absorption bands of tri- and tetravalent chromium ions and gives rise to a new absorption band in Mg2SiO4:Cr and Mg2SiO4:Cr,Li crystals heavily doped with chromium.

Interaction of impurity and intrinsic defects in forsterite and its role in the formation of spectral and luminescence properties

This paper reports on the results of investigations of the coefficients of chromium distribution between a crystal and a melt of forsterite, the absorption and luminescence spectra, and the electron paramagnetic resonance spectra of chromium centers in Mg2SiO4: Cr, Mg2SiO4: Cr: Sc, and Mg2SiO4: Cr: Li crystals. It has been established that the concentration dependences of these properties vary upon changing over from the range of trace concentrations of chromium, scandium, or lithium impurities in the melt to the range of higher concentrations of these impurities. The observed phenomenon is explained by the interaction of impurities with intrinsic defects of the crystal, which is called as the microimpurity trapping effect. According to the performed estimations, the concentration of predominant intrinsic defects (magnesium Frenkel defects) in the forsterite crystals grown from the melt is equal to (7.5 ± 0.3) × 10−6 atomic fractions. The energy of the formation of magnesium Frenkel defects can be estimated as 4.2 ± 0.2 eV.

Spin-dependent recombination of defects in bulk ZnO crystals and ZnO nanocrystals as studied by optically detected magnetic resonance

Abstract Long-lasting (several hours) afterglow at helium temperatures was observed in ZnO nanocrystals, 36 nm in size, after switching off the UV excitation. A quenching of the afterglow intensity in the magnetic field was found, which appears because of the preferential orientation of the recombining spins along the field and the spin-dependence of the recombination. ODMR was detected as resonance increase in the afterglow intensity at saturation of the EPR transitions of defects, which take part in the recombination. Shallow donors and different types of acceptors responsible for the afterglow in Al doped ZnO nanocrystals were identified. ODMR of donors and Li acceptors was recorded via the afterglow of bulk ZnO:Li, which could last for about an hour. In the photoluminescence-detected ODMR of bulk ZnO:Li crystals exchange-coupled donor–acceptor pairs were observed in addition to the Li acceptor and donor signals. Exchange-coupled pairs dominated the ODMR spectra recorded on the photoluminescence of ZnO nanocrystals.