Molecular dynamics calculation on three lithium atoms in planar cluster model C150H30 for glassy carbon

As the preliminary step to elucidate the charge-discharge mechanism in the glassy carbon cathode of lithium (Li) secondary battery, the molecular dynamics (MD) calculation was applied at molecular mechanics 2 (MM2) level for three Li atoms stabilized in the form of regular triangle in the central area of the hydrogen terminated planar cluster, C₁₅₀H₃₀. The stabilized Li sites are given on the basis of the structural optimization. Up to 10 K, the triangular Li aggregate kept at almost the same figure as that formed by three stabilization sites, rotating parallel to the cluster plane, goes around the central area of it, whereupon interatomic vibrational stretching is observed. Below 75 K, the aggregate of three Li atoms separates to a pair of two atoms and one Li atom arbitrarily, however, reformation of the pair occurs periodically among three atoms with the lapse of simulation time. Then, three Li atoms move correlatively irrespective of the long interatomic distance of 18 Å at maximum. However, at 100 K one Li atom goes out of the cluster model directly and the rest of two atoms continues the revolutional movement with the rotation as a pair in the central area of the cluster model. Thus, three Li atoms show the appreciably stable movements in the glassy carbon by forming the aggregate or the atomic pair, which will be responsible for the hysteresis in the charge-discharge cycle of lithium secondary battery.     

Field-induced transfer of lithium in a scanning tunneling microscope

Field-induced transfer of Li atoms from a [110]-oriented W tip to a Pt sample is realized in the scanning tunneling microscope (STM) under UHV conditions, using a working principle of the new solid state Li surface diffusion metal ion source (Li-SDMIS), in which the supply of Li to the apex of the tip occurs via surface diffusion. By applying 5–10 μs voltage pulses to the Li-covered W tip placed within tunneling range, single Li hillocks (400 × 400 Ų) were formed on the chosen area of the Pt(110) sample in a well-rep way. The pulse magnitude necessary for Li emission displays a distinct threshold character. A comparative analysis of the energetics of Li field desorption in the STM and Li-FDM (lithium field desorption microscope) modes indicates chemically-assisted field desorption of Li as the field-induced transfer mechanism.     

Al(111)/Al_3Li(111)的界面性质

运用基于第一性原理的平面波贋势法,计算研究了Al (111)/Al_3Li (111)的界面性质.结果表明:Al (111)/Al_3Li (111)的界面具有三种原子配位关系结构,其中界面处仍保持与基体Al一致的三明治堆垛构型的界面稳定性最好.计算表明,该结构界面最薄弱层,位于Al_3Li (111)内,其分离功最小(约1.53 J/m~2),强度最弱,而基体Al和Al_3Li内部的强度随着到界面距离的增大而逐渐增强.     

Pharmacokinetics of lithium in rat brain regions by spectroscopic imaging

Lithium (Li) and its salts have been demonstrated to be the most effective drug in both acute and prophylactic treatment of bipolar disorder. The exact molecular mechanisms and particular target regions accounting for its mood-stabilizing effect remain unknown. Knowledge of Li distribution and its regional pharmacokinetic properties in the living brain is of value in localizing its action in the brain. Pharmacokinetic measurements in different anatomical regions of the human brain are not yet available. Limited pharmacokinetic measurements in rat brain subvolumes have been performed using atomic absorption technique. However, a noninvasive way of estimating the pharmacokinetics in different regions of the brain where the drug exerts its beneficial effects would allow such methods to be used in the study of patients undergoing Li therapy. Earlier (7)Li MR studies on rat brain regions have provided preliminary pharmacokinetic information from the whole brain. Using (7)Li MR spectroscopic imaging (SI) technology, Li distribution in brain regions of the rat at therapeutic dosages has been recently demonstrated by us. Here we report feasibility of local pharmacokinetic measurements on brain regions obtained by magnetic resonance SI technology. Our results suggest that Li is most active in a region stretching from the anterior cingulate cortex and striatum to the caudal midbrain, with greatest activity including the preoptic area and hypothalamic region. Some activity was seen in prefrontal cortex, but only minimal amounts in the region of the cerebellum and metencephalic brainstem.     

液态锂在铜的微通道中的流动行为

本文采用分子动力学方法模拟了液态锂在铜的微通道内的流动行为. 通过构建铜(111), (100)和(110)晶面的微通道内壁, 研究了液态锂在流固界面上的微观结构以及在铜微通道中的流动速度分布情况, 并探讨了微通道尺寸对液态锂流动行为的影响. 研究结果表明铜微通道内的液态锂在靠近铜固体壁附近区域呈有序的层状结构分布, 并受铜内壁晶面微观结构的影响. 铜(111)和(100)面内壁附近的液态锂有序层分布结构更明显. 外驱力作用下的液态锂在微通道内的流动速度呈抛物线分布, 流固界面和流动方向对液态锂的流动速度都会产生影响. 液态锂在铜(111)面内壁上流动的速度最大, 且出现了速度滑移; 在铜(110)面内壁上流动速度最小. 通过对不同尺寸的微通道内液态锂流动行为的研究, 发现流动速度的大小随着微通道尺寸的增加而增大, 且最大速度与微通道尺寸呈二次函数关系, 与有关理论计算结果符合得很好.     

Formation of positive cluster ions Li(n) Br (n = 2-7) and ionization energies studied by thermal ionization mass spectrometry

Clusters of the type Li(n)X (X = halides) can be considered as potential building blocks of cluster-assembly materials. In this work, Li(n)Br (n = 2-7) clusters were obtained by a thermal ionization source of modified design and selected by a magnetic sector mass spectrometer. Positive ions of the Li(n)Br (n = 4-7) cluster were detected for the first time. The order of ion intensities was Li(2)Br(+) > Li(4)Br(+) > Li(5)Br(+) > Li(6)Br(+) > Li(3)Br(+). The ionization energies (IEs) were measured and found to be 3.95 ± 0.20 eV for Li(2)Br, 3.92 ± 0.20 eV for Li(3)Br, 3.93 ± 0.20 eV for Li(4)Br, 4.08 ± 0.20 eV for Li(5)Br, 4.14 ± 0.20 eV for Li(6)Br and 4.19 ± 0.20 eV for Li(7)Br. All of these clusters have a much lower ionization potential than that of the lithium atom, so they belong to the superalkali class. The IEs of Li(n)Br (n = 2-4) are slightly lower than those in the corresponding small Li(n) or Li(n)H clusters, whereas the IEs of Li(n)Br are very similar to those of Li(n) or Li(n)H for n = 5 and 6. The thermal ionization source of modified design is an important means for simultaneously obtaining and measuring the IEs of Li(n)Br (n = 2-7) clusters (because their ions are hermodynamically stable with respect to the loss of lithium atoms in the gas phase) and increasingly contributes toward the development of clusters for practical applications.     

New mass value for 7Li

A high-accuracy mass measurement of 7Li was performed with the SMILETRAP Penning-trap mass spectrometer via a cyclotron frequency comparison of 7Li3+ and H2+. A new atomic-mass value of 7Li has been determined to be 7.016 003 425 6(45) u with a relative uncertainty of 0.63 ppb. It has uncovered a discrepancy as large as 14sigma (1.1 microu) deviation relative to the literature value given in the Atomic-Mass Evaluation AME 2003. The importance of the improved and revised 7Li mass value, for calibration purposes in nuclear-charge radii and atomic-mass measurements of the neutron halos 9Li and 11Li, is discussed.     

HI-13串列加速器生物用新终端7Li离子束流监测诊断研究

7Li离子属于高LET辐射,是辐射生物学基础研究中常用的重离子射线之一,它是硼中子俘获治疗癌症中起关键作用的离子,在辐射诱变育种等领域也有较好的应用前景。实验在北京HI-13串列加速器R20支线生物用新终端上进行,对43 MeV 7Li离子束斑大小、均匀性和监测注量的准确性进行测量和评估,结果表明:均匀性好于90%的最大束斑面积为5.0cm×5.0cm;4.2×104 ～1.5×105 particles/cm2/s注量率范围内,两种不同探测器测得的注量率变化呈线性关系,闪烁体探测器监测的注量与CR39探测器测得的绝对注量的误差小于10%。这些束流特性能够满足辐射生物学实验要求,有利于进一步开展与硼中子俘获治疗癌症或辐射诱变育种中7Li离子的辐射生物学相关研究。7Li ion with high linear energy transfer (LET) radiation has been used in radiobiological research, takes main effect in Boron Neutron Capture Therapy and is applied in radiation mutagenic breeding. This experiment was carried on the new terminal established for radiobiological application, located at the end of R20 branch beam line of HI-13 tandem accelerator. The beam qualities of 7Li ions of 43MeV generated by HI-13 tandem accelerator, including spot size and uniformity and particle fluence accuracy were measured using different detection methods. The results showed that beam uniformity was over 90% at 5cm×5cm area, the flux of S1 and M3 had a good linear relationship as particle flux ranged from 4.2×104 particles/cm2/s to 1.5×105 particles/cm2/s, and particle fluence accuracy was better than 90%. All the results showed that the beam qualities of 7Li ions finely met the basic requirements for radiation biological experiment. It provides important method to study biological effects for fundamental research and tumor therapy or radiation mutagenic breeding application associated with 7Li ions.     

CO2 capture by Li‐functionalized silicene

CO₂ capture and storage technology is of key importance to reduce the greenhouse effect. By its large surface area and sp³ hybridization, Li‐functionalized silicene is demonstrated to be a promising CO₂ absorbent that is stable up to at least 500 K and has a very high storage capacity of 28.6 mol/kg (55.7 wt%). The adsorption energy of CO₂ on Li‐functionalized silicene is enhanced as compared to pristine silicene, to attain an almost ideal value that still facilitates easy release. In addition, the band gap is found to change sensitively with the CO₂ coverage. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Investigations of Li-containing SiCN(O) ceramics via 7Li MAS NMR

Lithium-containing silicon (oxy)carbonitride ceramics (SiCN(O):Li) were synthesized via precursor-to-ceramic-transformation of Li-containing (poly)silazanes. The precursors were obtained by lithiation of 2,4,6-trimethyl-2,4,6-trivinylcyclotrisilazane with n-butyllithium and by reaction of a commercial poly(organosilazane) VL20 with metallic lithium. The annealing treatment was carried out at temperatures between 200 and 1400 degrees C in argon (DeltaT=200 degrees C) and yielded Li-containing silicon (oxy)carbonitride. X-ray powder diffraction revealed that the resulting SiCN(O):Li ceramics were basically amorphous up to temperatures of 1000 degrees C and formed LiSi(2)N(3), graphite and silicon carbide as crystalline phases at higher temperatures. (7)Li MAS NMR spectroscopy was carried out to investigate the structure of the Li-containing phases and to study the reaction path of metallic Li with polysilazane. Based on the NMR spectra, there is almost no difference found in the chemical shift of the SiCN(O):Li ceramics obtained at different temperatures. Accordingly, Li is assigned to be mainly coordinated to N and O present as contaminant element. Relaxation time measurements showed that the most mobile Li(+) species seems to be present in the product obtained in the pyrolysis temperature range between 600 and 1000 degrees C.     

Measurement of the ~2H(~7Be,~6Li)~3He reaction rate and its contribution to the primordial lithium abundance

In the standard Big Bang nucleosynthesis(SBBN) model, the lithium puzzle has attracted intense interest over the past few decades, but still has not been solved. Conventionally, the approach is to include more reactions flowing into or out of lithium, and study the potential effects of those reactions which were not previously considered.~7Be(d,~3He)~6Li is a reaction that not only produces~6Li but also destroys~7Be, which decays to~7Li, thereby affecting~7Li indirectly. Therefore, this reaction could alleviate the lithium discrepancy if its reaction rate is sufficiently high.However, there is not much information available about the~7Be(d,~3He)~6Li reaction rate. In this work, the angular distributions of the~7Be(d,~3He)~6Li reaction are measured at the center of mass energies Ecm = 4.0 Me V and 6.~7Me V with secondary~7Be beams for the first time. The excitation function of the~7Be(d,~3He)~6Li reaction is first calculated with the computer code TALYS and then normalized to the experimental data, then its reaction rate is deduced. A SBBN network calculation is performed to investigate its influence on the~6Li and~7Li abundances. The results show that the~7Be(d,~3He)~6Li reaction has a minimal effect on~6Li and~7Li because of its small reaction rate. Therefore,the~7Be(d,~3He)~6Li reaction is ruled out by this experiment as a means of alleviating the lithium discrepancy.     

Li(2P)+H_2→LiH+H反应截面的测量

在样品池条件下,用脉冲激光670.8 nm线激发Li原子基态至2P态,测量了的反应碰撞能量转移截面。池温保持在888 K,Li原子密度为10~(13)cm~(-3)量级,而H_2气压控制在60～300 Pa之间,测量时间分辨荧光光谱,它由两部分组成,在脉冲激光激发的瞬间(不超过10 ns),荧光迅速增强至最大值;激发结束后,荧光强度按指数衰减,由衰减曲线得到2P态原子在不同H_2气压下的有效寿命。根据Stern-Volmer方程,有效寿命与H_2气压成线性关系,由该直线的斜率给出了总的猝灭截面(25.1±4.0)×10~(-16)cm~2,而从直线的截距得到辐射寿命为(270±54)ns。总的猝灭截面是反应与非反应碰撞截面之和,由在不同H_2气压下记录的瞬态(10 ns)荧光快速增强信号得到反应截面为(0.2±0.1)×10~(-16)cm~2,虽只占总猝灭截面的1/125,但它在Li(2P)+H_2的碰撞传能中所起的作用是不能略去的。     

熔盐对Li+/Na+离子交换及折射率分布的影响

研究发现利用Li⁺/Na⁺离子交换制取径向梯度折射率(GRIN)棒透镜时,在NaNO₃熔盐中,添加NaCl,会影响Li⁺/Na⁺离子交换反应平衡,最终改变径向GRIN棒透镜的折射率分布、折射率差值及像差.并着重分析和讨论了在本实验中NaNO₃+NaCl混合熔盐对径向GRIN棒透镜中折射率分布、数值孔径及像差的影响机理.     

Vacancy-driven anisotropic defect distribution in the battery-cathode material LiFePO4

Li-ion mobility in LiFePO(4), a key property for energy applications, is impeded by Fe antisite defects (Fe(Li)) that form in select b-axis channels. Here we combine first-principles calculations, statistical mechanics, and scanning transmission electron microscopy to identify the origin of the effect: Li vacancies (V(Li)) are confined in one-dimensional b-axis channels, shuttling between neighboring Fe(Li). Segregation in select channels results in shorter Fe(Li)-Fe(Li) spans, whereby the energy is lowered by the V(Li)'s spending more time bound to end-point Fe(Li)'s. V(Li)-Fe(Li)-V(Li) complexes also form, accounting for observed electron energy loss spectroscopy features.     

Identification by TEM and EELS of the products formed at the surface of a carbon electrode during its reduction in MClO4-EC and MBF4-EC electrolytes (M = Li, Na)

The electrochemical intercalation of lithium and sodium into graphite was carried out using a liquid electrolyte containing ethylene carbonate (EC) as solvent and MClO4 or MBF4 (M = Li, Na) as salts. The first intercalation of alkali metals into graphite is accompanied with irreversible reactions attributed to the reduction of the electrolyte. These reactions contribute to the development of a passivating layer, formed on graphite surface prior to intercalation. This layer is impervious to solvent molecules but allows alkali ions to diffuse through its bulk. The surface chemistry of the electrodes was characterized using transmission electron microscopy (image, selected area electron diffraction) as well as EELS. The effect of the nature of the alkali salts on the properties of the passivating layer is studied.     

Li原子修饰笼型Si6团簇的结构和储氢性能

利用杂化密度泛函B3LYP方法, 在6-311+G(d, p)基组水平上对Si6和Li修饰的Si6团簇的几何结构和电子性质及储氢性能进行模拟计算和理论研究. 结果表明, Si6团簇最低能量构型为笼型结构, 纯Si6团簇不能有效吸附氢分子. Li原子的引入显著改善了Si6团簇的储氢能力. 以两个Li原子端位修饰Si6团簇为载体, 其氢分子的平均吸附能为1.692~2.755 kcal/mol, 每个Li原子周围可以有效吸附五个氢分子, 储氢密度可达9.952wt%. 合适的吸附能和较高储氢密度表明Li修饰Si6团簇有望成为理想的储氢材料.     

Work function dependence of the Li(2p) formation in slow collisions of Li atoms with partially cesiated tungsten surfaces

The reflection of Li atoms from partially cesiated polycrystalline tungsten is studied at impact energies between 100 and 1000 eV at near-grazing incidence angles. The work function dependence of the yield for Li(2p) formation is studied between φ = 1.27 and 4.8 eV together with the probability for Li⁺ formation. While Li⁺ formation is only important for φ > 3.5 eV, the probability for Li(2p) excitation has its maximum of several percents near (at φ = 1.7±0.1 eV), but not exactly at the minimum of the work function. The dependence of the absolute photon yield is given as a function of the impact energy. The polarization properties of the Li(2p → 2s) photons are also studied. The angular distribution of the excited Li(2p) atoms for various φ values is obtained by applying photon-scattered atom coincidence techniques. An effort is made to understand the Li(2p) formation on cesiated metal surfaces on the basis of the nonadiabatic coupling between different Li states induced by the motion of the Li atom relative to the surface.     

Li原子修饰笼型Si_6团簇的结构和储氢性能

利用杂化密度泛函B3LYP方法,在6-311+G(d,p)基组水平上对Si_6和Li修饰的Si_6团簇的几何结构和电子性质及储氢性能进行模拟计算和理论研究.结果表明,Si_6团簇最低能量构型为笼型结构,纯Si_6团簇不能有效吸附氢分子.Li原子的引入显著改善了Si_6团簇的储氢能力.以两个Li原子端位修饰Si_6团簇为载体,其氢分子的平均吸附能为1.692~2.755 kcal/mol,每个Li原子周围可以有效吸附五个氢分子,储氢密度可达9.952 wt%.合适的吸附能和较高储氢密度表明Li修饰Si_6团簇有望成为理想的储氢材料.     

The ionic conductivity in lithium-boron oxide materials and its relation to structural, electronic and defect properties: insights from theory

We review recent theoretical studies on ion diffusion in (Li(2)O)(x)(B(2)O(3))(1-x) compounds and at the interfaces of Li(2)O :B(2)O(3) nanocomposite. The investigations were performed theoretically using DFT and HF/DFT hybrid methods with VASP and CRYSTAL codes. For the pure compound B(2)O(3), it was theoretically confirmed that the low-pressure phase B(2)O(3)-I has space group P3(1)21. For the first time, the structure, stability and electronic properties of various low-index surfaces of trigonal B(2)O(3)-I were investigated at the same theoretical level. The (101) surface is the most stable among the considered surfaces. Ionic conductivity was investigated systematically in Li(2)O, LiBO(2), and Li(2)B(4)O(7) solids and in Li(2)O:B(2)O(3) nanocomposites by calculating the activation energy (E(A)) for cation diffusion. The Li(+) ion migrates in an almost straight line in Li(2)O bulk whereas it moves in a zig-zag pathway along a direction parallel to the surface plane in Li(2)O surfaces. For LiBO(2), the migration along the c direction (E(A) = 0.55 eV) is slightly less preferable than that in the xy plane (E(A) = 0.43-0.54 eV). In Li(2)B(4)O(7), the Li(+) ion migrates through the large triangular faces of the two nearest oxygen five-vertex polyhedra facing each other where E(A) is in the range of 0.27-0.37 eV. A two-dimensional model system of the Li(2)O :B(2)O(3) interface region was created by the combination of supercells of the Li(2)O (111) surface and the B(2)O(3) (001) surface. It was found that the interface region of the Li(2)O:B(2)O(3) nanocomposite is more defective than Li(2)O bulk, which facilitates the conductivity in this region. In addition, the activation energy (E(A )) for local hopping processes is smaller in the Li(2)O :B(2)O(3) nanocomposite compared to the Li(2)O bulk. This confirms that the Li(2)O:B(2)O(3) nanocomposite shows enhanced conductivity along the phase boundary compared to that in the nanocrystalline Li(2)O.     

Absolute transition frequencies and quantum interference in a frequency comb based measurement of the (6,7)Li D lines

Optical frequencies of the D lines of (6,7)Li were measured with a relative accuracy of 5 × 10?11 using an optical comb synthesizer. Quantum interference in the laser induced fluorescence for the partially resolved D2 lines was found to produce polarization dependent shifts as large as 1 MHz. Our results resolve large discrepancies among previous experiments and between all experiments and theory. The fine-structure splittings for ?Li and ?Li are 10052.837(22) MHz and 10053.435(21) MHz. The splitting isotope shift is 0.599(30) MHz, in reasonable agreement with recent theoretical calculations.