Carbon‐Coated Supraballs of Randomly Packed LiFePO4 Nanoplates for High Rate and Stable Cycling of Li‐Ion Batteries

One of the key strategies used to obtain high‐rate Li‐ion battery is the reduction of the Li‐ion path length inside the active materials and the enhancement of the ionic diffusion outside the active materials. It is demonstrated that electrochemical performance can be improved significantly at high C‐rates using carbon‐coated spherical aggregates or “supraballs” of randomly packed olivine LiFePO₄ (LFP) nanoplates as cathode active materials. 258 nm LFP nanoplates with 30 nm thickness are synthesized through a high‐temperature solvothermal method, in which short lithium‐ion channels are formed perpendicular to the top or bottom planes. These thin nanoplates are formed into carbon‐coated “supraballs” through a spray‐drying and thermal annealing process, in which nanoplates are not stacked but randomly packed due to relatively fast drying. Internal and external nanoplate ion diffusion is therefore enhanced simultaneously due to the optimal molecular crystalline structure and interparticle pore structures of the nanoplates. Indeed, the initial capacity of the carbon‐coated supraballs is 162 mAh g^?1 (173.34 mAh cm^?3) at 0.1 C and more than 80% is retained (≈130.91 mAh g^?1) at 50 C. Furthermore, they offer durable cycling stability (>500 cycles) at 1 C without compromising their capacity.     

Optical pumping of ions in buffer gases

Transient signals measured with a pulsed rf-optical pumping method are used to determine longitudinal relaxation rates for Sr⁺ ions (even isotopes) in noble gas buffers. Depolarization cross sections of the electronic spin in the Sr⁺5² S _1/2 ground state for binary collisions with rare gas atoms are deduced. The results for σ(Sr⁺5² S _1/2) in Ų are (at temperatures between 374 and 449 °K): 2·10^?5(He),4·10^?5(Ne), 5.7·10^?3(Ar), 1.8·10^?2(Kr), and 4.0·10^?2(Xe). These cross sections for the Sr⁺ ion are about two to three orders of magnitude larger than the corresponding ones for the isoelectronic neutral Rb atom. The large increase of the Sr⁺ relaxation rates is explained with the relaxation mechanism of spin-orbit coupling, taking into account two “indirect” effects of the ionic charge: the increase in the gas kinetic cross sections and the more intimate collisions of the Sr⁺ ion with the noble gas atoms. The depolarization is shown to be predominantly due to short-range interactions. A contribution to the relaxation of the Sr⁺ ion from Sr⁺-noble gas molecule formation, induced by three-body or resonant two-body collisions, could not be established for applied pressuresp between 1.5 and 15 Torr of Ar, Kr, and Xe.     

Interaction of hydrogen and deuterium with intrinsic atomic defects in high-purity electron-irradiated nickel

Abstract

High-purity nickel was irradiated with 2 MeV electrons at temperatures below 80 K to a dose of 1 × 10²³ e^?/m² in the as-prepared state and after charging with H or D. By means of magnetic after-effect measurements relaxations of anisotropic radiation-induced defects and of defect-hydrogen complexes were investigated in the temperature range between 4.2 and 500 K. The isochronal annealing behaviour of these relaxations and the isochronal recovery of the residual resistivity was measured simultaneously on the same specimens. At temperatures below the hydrogen mobility (< 160 K) in charged irradiated specimens relaxation maxima are observed at 45, 100, 115 and 140 K which show no isotope shift for H and D charging. The maxima below 160 K are explained by defect-hydrogen complexes, where radiation-induced defects reorient around immobile hydrogen atoms. Above 160 K, where hydrogen atoms get mobile, in charged irradiated specimens a broad relaxation maximum appears at 170 K which shows an inverse isotope shift for H and D charging. This 170 K maximum anneals in Stage III. A hydrogen diffusion maximum observed in charged specimens at 215 K prior to irradiation is missing after electron irradiation. The 170 K relaxation is explained by defect-hydrogen complexes, where hydrogen atoms reorient around immobile radiation-induced defects while the long-range hydrogen diffusion is suppressed by these defects. In such relaxation measurements hydrogen and deuterium atoms are used as a “probe” to investigate radiation-induced defects.     

Nuclear spin relaxation,hybridization, and low-temperature 4f spin fluctuations in intermediate-valent SmB6

¹¹B spin-lattice relaxation measurements have been carried out in SmB₆ samples with large low-temperature resistivities. Above 15 K the relaxation is activated, with approximately the same gap (≈6 meV) as found previously in transport and optical measurements. 4f spin fluctuations apparently dominate the relaxation, so that these results give strong evidence for 4f-conduction band hybridization at the gap edge. An anomalous peak in the relaxation rate was observed at ≈5 K, which is tentatively attributed to fluctuations of “remagnetized” Sm³⁺ ions near Sm-site vacancies.     

Thermodynamic properties of successive phase transitions in Rb2ZnBr4

Heat capacity measurements have given the following transition temperatures and entropies: 0.027 J K^?1mol^?1 at 76.5 K, 0.47 J K^?1mol^?1 at 111.7 K, and 0.048 J K^?1mol^?1 at 193.6 K. These are interpreted as “lock-in”, soft-mode, and “lock-in” transitions, respectively, from comparison with analogous results for Rb₂ZnCl₄ and K₂SeO₄. The N-IC transition was located at 347 K by DTA.     

13C- and 1H-NMR Relaxation Investigation of a Polyciclic Nitrogen Compound: 3,3-Dimethyl-1,5-diphenyl-9-hydroxy-bispidinium Iodide

The rigid polycyclic nitrogen compound was considered as a test for the reliability of internuclear distances calculated by ¹H-NMR spin-lattice relaxation rates. The ‘isotropic’ motional correlation time was calculated from ¹³C relaxation rates (τ_C = 0.11 ns at 298 K). Dipolar cross-relaxation rates were calculated by measuring non-, mono- and double-selective proton spin-lattice relaxation rates. All the experimental relaxation rates were thoroughly accounted for by dipolar pairwise interactions. Only at high temperatures a certain contribution from the spin rotational mechanism was apparent.     

Dynamics of SCN- ions in molten thiocyanates and aqueous solutions by Raman spectroscopy

The Raman spectra of the v ₁(CN) stretching mode of SCN^- ions have been measured in molten thiocyanates, KSCN and NaSCN, at temperatures 450-600K. The vibrational and the rotational correlation functions are calculated, and the dynamics of SCN^- ions in the molten state are compared with those in aqueous solutions of KSCN, NaSCN, and LiSCN at concentrations 1–10 mol dm^-3 and at temperatures 303–353 K. The observed vibrational correlation functions are analysed by the stochastic line shape theory of Kubo, in which homogeneous and inhomogeneous broadening are treated simultaneously. Both broadening contributions to the isotropic spectra are extracted. The homogeneous broadening is found to increase with increasing temperature in both melts and aqueous solutions; the inhomogeneous broadening remains constant in molten KSCN while it decreases in aqueous solutions. As the result, the isotropic Raman bandwidth is considered to increase with temperature in the molten state and to decrease in aqueous solutions. Rotational correlation functions of SCN^- ions in these molten salts show the behaviour of the short time inertial rotation (t ? 0·15 ps, jump angle 20°), which is a little slower than the free rotation of a single ion. The long time exponential decay of the rotational correlation functions reflects the ultimate diffusional behaviour of the ionic reorientation. The rotational relaxation rate increases with increasing temperature in both melts and aqueous solutions. The vibrational dephasing rate decreases and the rotational relaxation rate increases as the cation size increases in melts. In aqueous solutions, the vibrational dephasing rate follows the same cation dependence as that in melts, while the rotational relaxation rate decreases as the cation size increases. This seems to be a consequence of the specific local structures in aqueous electrolyte solutions.     

The SrB4O7:Sm2+ optical sensor and the pressure homogeneization through thermal cycles in diamond anvil cells

Abstract

Preliminary results, up to 550 kbar, on a thermal-cycling relaxation process of the 4.Methanol-1.Ethanol pressure-transmitting medium, are presented. The homogeneization is monitored by linewidth measurements of the ⁵D₀-⁷F₀ emission line of SrB₄O₇:Sm²⁺, recently proposed as an “almost ideal” high pressure calibrant. Above 100 kbar at 20°C, the line broadens linearly with increaisng pressure. Upon heating, at a fixed pressure, the linewidth is reduced to a minimum (“hydrostatic”) value provided a sufficient temperature is reached and this narrowing is irreversible upon cooling. For T=300°C this relaxation is observed for P (250 kbar, incomplete at 340 kbar and not observed at 550 kbar.     

Kondo scattering and properties of TmSe in the infrared region

The conductivity and permittivity spectra of the intermediate-valence semiconductor TmSe have been measured by terahertz and infrared spectroscopy in a frequency range of 10–10⁴ cm^?1 and a temperature range of 5–300 K. At low temperatures (5 K < T < 100 K), the spectra contain a gap Δ ≈ 2.5 meV, whose appearance is considered to be related to conduction-electron localization at local magnetic moments. At high temperatures (100 K < T < 300 K), the dielectric response is specified by two electronic components: “ light” conduction electrons and “heavy” hybridized f-d states. The microscopic parameters of both components, such as the concentration, mobility, effective mass, relaxation frequency, and the plasma frequency, are determined.     

金属玻璃Ni30Zr70的动态粘度和稳态粘度

本文测量了金属玻璃Ni₃₀Zr₇₀的动态粘度和稳态粘度,结果表明,由于结构弛豫的影响,动态粘度随升温速率的减小而线性增加,在玻璃转变温度T_g以下,动态粘度与温度的关系可以用Arrhenius方程进行描述,稳态粘度与温度的依赖关系满足Fulcher-Vogel方程。从4种不同升温速率的高温(结晶开始温度T_x)动态粘度值,给出金属玻璃Ni₃₀Zr₇₀的平衡粘度。在630—670K     

Charge carrier concentration in glasses. dependence on composition

Admittance spectra of the ion conducting glasses xNa₂O(1−x)SiO₂ and xK₂O(1−x)SiO₂,(x=0,1–0,3) have been studied on small signal conditions from room temperature to 713 K. Conductivity relaxation in the bulk and space charge relaxation due to drift and diffusion near the electrodes were found in separated parts of the frequency range 10⁻⁴–10⁶ Hz. The data show Arrhenius behaviour for dc conductivity and conductivity relaxation. The determination of the charge carrier concentration is based on the analysis of the beginning of space charge relaxation. The free carrier concentration, n₀, were evaluated to be of the order of 10²³ m⁻³ at temperatures 400 – 700 K and show a weak dependence on composition. The dominant factor determining conductivity was mobility in these glasses. The strong temperature dependence of n₀ below 400 K indicates changed conditions for the development of the space charge relaxation which are discussed. Paper presented at the 1st Euroconference on Solid State Ionics, Zakynthos, Greece, 11–18 Sept. 1994.     

NMR proton relaxation and chemical exchange in the system H16 2O/H17 2O-[2H6]dimethylsulphoxide

NMR proton relaxation rates of normal and ¹⁷O enriched water in a mixture of 68 mol% water and 32 mol% [²H₆]dimethylsulphoxide were measured for temperatures between 298 K and 183 K. In the range between 240 K and 204 K the limit of fast proton-proton exchange between H¹⁶ ₂O and H¹⁷ ₂O is not obeyed, and relaxation curves deviate from mono-exponential behaviour. By fitting the relaxation curves to a model of NMR two-phase relaxation the proton-proton exchange rate within the aqueous component could be obtained. With decreasing temperature, proton-proton exchange slows down and a residence time of about 125 ms at 215 K is found, but it becomes faster again for still lower temperatures. From the phase-averaged relaxation rates of water in the ¹⁷O enriched mixtures, the ¹⁷O induced proton relaxation rate was derived as a function of temperature. This yields the rotational correlation times of the water molecule in the mixture and the dipolar spin-lattice coupling parameter. The latter is considerably lower than the one predicted from the geometry of water.     

Dynamics of muons in the ferroelectric material KDP

Muon spin relaxation in zero field and longitudinal field was measured in single crystal samples of KH₂PO₄ (KDP) and KD₂PO₄ (DKDP) over a temperature range of 5 K to 300 K. At low temperatures, diamagnetic muons and muon substituted radicals with nuclear hyperfine coupling can be observed. For both KDP and DKDP, a minor change was observed in the dynamics of the muon below 140 K. Above 140 K, the mobility of the muon appears to increase and the diffusion rate becomes faster with increasing temperature. Only a small increase in the relaxation rate is observed in KDP due to the presence of theH ⁺, suggesting that the relaxation effects probably originate from the³¹P.     

Modelling the voltammetric study of intercalation in a host structure: application to lithium intercalation in RuO2

Intercalation process kinetics have been studied theoretically for the case of potential sweep voltammetry. The influence of the thickness (or the particle radius) of the “host” material and the potential sweep rate has been determined between the limits of thin film diffusion and semi-infinite diffusion for a reversible process. Experimental data have been obtained with the cell: RuO₂/LiClO₄-PEO/Li. The theoretical results have been used to calculate the diffusion coefficient of lithium in the “host” structure RuO₂ at 80°C, giving an approximate value of 1.6 × 10^?11 cm² s^?1     

Spin lattice relaxation of F+ centers in neutron irradiated cao crystals

Abstract

We have measured the electron spin-lattice relaxation rates of F⁺ centers in CaO crystals at different F⁺ centers concentrations (from 5.8·10¹⁵ to 1.4·10¹⁷ cm^?3) in magnetic fields from 10^?3 to 4.8 T and temperatures from 0.4 to 4.2 K. At temperatures above 1 K the relaxation rate is nearly proportional to the F⁺ centers concentration. Spin diffusion to fast relaxing centers is essential in determining the F⁺ centers spin polarization decay.     

19F nuclear spin relaxation and spin diffusion effects in the single-ion magnet LiYF4:Ho3+

Temperature and magnetic field dependences of the ¹⁹F nuclear spin-lattice relaxation in a single crystal of LiYF₄ doped with holmium are described by an approach based on a detailed consideration of the magnetic dipole-dipole interactions between nuclei and impurity paramagnetic ions and nuclear spin diffusion processes. The observed non-exponential long time recovery of the nuclear magnetization after saturation at intermediate temperatures is in agreement with predictions of the spin-diffusion theory in a case of the diffusion limited relaxation. At avoided level crossings in the spectrum of electron-nuclear states of Ho^{3 +} ions, rates of nuclear spin-lattice relaxation increase due to quasi-resonant energy exchange between nuclei and paramagnetic ions in contrast to the predominant role played by electronic cross-relaxation processes in the low-frequency ac-susceptibility.     

Li and K NMR relaxation study of a LiKSO4 single crystal

The ⁷Li and ³⁹K NMR relaxations in a LiKSO₄ single crystal grown by the slow evaporation method were investigated by employing a pulse NMR spectrometer. From the experimental data, the quadrupole coupling constant and asymmetry parameter were determined at the temperatures of 180 and 300 K. The relaxation processes of ⁷Li and ³⁹K were studied for the LiKSO₄ crystal, and the relaxation times for the ⁷Li and ³⁹K nuclei exhibit remarkable changes near T_c2 (=190 K). The activation energies for ⁷Li and ³⁹K were determined in phases I and III. The large change in the activation energy at 190 K indicates that the Li and K ions are significantly affected during this transition. The correlation time of the ⁷Li calculated from the spin-lattice relaxation time and quadrupole parameters was larger than that of the ³⁹K calculated using the same method. The reason for this is that the Li ion undergoes molecular motion as in the LiO₄ groups.     

Dispersion of dielectric constants in bismuth strontium ferrite (Bi,Sr)FeO<Subscript>3 − <Emphasis Type="Italic">x</Emphasis></Subscript>—Variable-valence perovskite-structure solid solution

The reflection spectrum R(ν) and transmission spectrum Tr(ν) of polycrystalline solid solutions Bi_0.5Sr_0.5FeO_2.75 are studied for the first time using submillimeter and IR spectroscopy in the frequency range 7 < ν < 4000 cm^?1 at temperatures of 10–300 K. A large difference is found between the magnitudes of the dielectric susceptibility measured by contact (at a frequency of 10³ Hz) and noncontact (THz range) methods. It is suggested that powerful relaxation excitations exist at frequencies below 100 cm^?1 (“subphonon” region). The possible origin of the excitations is discussed.     

Lineshapes of the 172 and 602 GHz rotational transitions of HCN

Experimental lineshapes of the 172 and 602 GHz millimeter lines of HC¹⁵N in collision with H₂, N₂, O₂, CH₃CN and some rare gases are studied for the purpose of atmospheric applications and detailed collision analysis. Using of a sensitive frequency modulation technique allows highlighting clear deviations from the usual Voigt profile, these departures being generally considered as related to molecular diffusion effects or to the dependence of collisional relaxation rates on molecular speeds. Except the light buffer gases H₂ and He, the linefits using the Galatry profile lead to nonlinear pressure dependencies of relaxation rates, that rules out the frequent hypothesis of an exclusive role of molecular diffusion (Dicke effect). This observation is shown to be in accordance with the fact that optical radii related to relaxation are usually greater than kinetic Lennard-Jones radii tied to diffusion. In contrast, the actual lineshapes are well reproduced by the Speed-Dependent Voigt profile taking into account the speed dependence of relaxation rates which display linear pressure dependencies. For the particular cases of the N₂- and Ar-HCN pairs, the experimental results are rather well explained by semi-classical computations based on the Robert–Bonamy formalism improved by the model of exact trajectories. These computations show that relaxation rates are proportional to some power of the colliders’ relative speed. A detailed comparison of relaxation parameters deduced from low-pressure experiments with Galatry and Speed-Dependent Voigt profiles allows to infer that the optical diffusion rates are much smaller that kinetic ones, so that the experimental lineshapes depend nearly exclusively on the speed dependence of relaxation rates and are weakly affected by molecular diffusion effects. Extension of these conclusions to other molecules of atmospheric interest is discussed. Finally, an appendix presents unpublished results dealing with the collisional relaxation of some rotational lines of HC¹⁵N (at 258 GHz for different temperatures and at 344 GHz) and HC¹⁴N (at 355 GHz).     

<Superscript>63,65</Superscript>Cu NMR study of low-frequency spin dynamics in the infinite-layer antiferromagnetic compound SrCuO<Subscript>2</Subscript>

The spin-lattice and spin-spin relaxation times have been measured for ^63,65Cu NMR in the infinite-layer anti-ferromagnet SrCuO₂ in the ordered state for temperatures from 4.2 to 361 K. In the region of low temperatures (T≤250 K), both relaxation processes are of the same nature and the main contribution to the relaxation rate is associated with the diffusion of a small number of holes with an activation energy of ～42 meV. In the high-temperature range (T > 250 K), contributions to the transverse relaxation rate exhibit redistribution and this relaxation process is determined predominantly by indirect interactions.