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1.
Several Li-Sn crystalline phases, i.e. Li2Sn5, LiSn, Li7Sn3, Li5Sn2, Li13Sn5, Li7Sn2 and Li22Sn5 were prepared by ball-milling and characterized by X-ray powder diffraction and 119Sn Mössbauer spectroscopy. The analysis of the Mössbauer hyperfine parameters, i.e. isomer shift (δ) and quadrupole splitting (Δ), made it possible to define two types of Li-Sn compounds: the Sn-richest compounds (Li2Sn5, LiSn) and the Li-richest compounds (Li7Sn3, Li5Sn2, Li13Sn5, Li7Sn2, Li22Sn5). The isomer shift values ranged from 2.56 to 2.38 mm s−1 for Li2Sn5, LiSn and from 2.07 to 1.83 mm s−1 for Li7Sn3, Li5Sn2, Li13Sn5, Li7Sn2 and Li22Sn5, respectively. A Δδ correlation diagram is introduced in order to identify the different phases observed during the electrochemical process of new Sn-based materials. This approach is illustrated by the identification of the phases obtained at the end of the first discharge of η-Cu6Sn5 and SnB0.6P0.4O2.9.  相似文献   

2.
The galvanostatic intermittent titration technique (GITT) has been used to electrochemically determine the chemical and component diffusion coefficients, the electrical and general lithium mobilities, the partial lithium ionic conductivity, the parabolic tarnishing rate constant, and the thermodynamic enhancement factor in “Li3Sb” and “Li3Bi” as a function of stoichiometry in the temperature range from 360 to 600°C. LiCl, KCl eutectic mixtures were used as molten salt electrolytes and Al, “LiAl” two-phase mixtures as solid reference and counterelectrodes. The stoichiometric range of the antimony compound is rather small, 7 × 10?3 at 360°C, whereas the bismuth compound has a range of 0.22 (380°C), mostly on the lithium deficit side of the ideal composition. The thermodynamic enhancement factor in “Li3Sb” depends strongly on the stoichiometry, and has a peak value of nearly 70 000; for “Li3Bi” it rises more smoothly to a maximum of 360. The chemical diffusion coefficient for “Li3Sb” is 2 × 10?5 cm2 sec?1 at negative deviations from the ideal stoichiometry and increases by about an order of magnitude in the presence of excess lithium at 360°C. The corresponding value for “Li3Bi” is 10?4 cm2 sec?1 with high lithium deficit, and increases markedly when approaching ideal stoichiometry. The activation energies are small, 0.1–0.3 eV, depending on the stoichiometry, in both phases. The mobility of lithium in “Li3Bi” is about 500 times greater than in “Li3Sb” with a lithium deficit. The ionic conductivity in “Li3Sb” increases from about 10?4 Ω?1 cm?1 in the vacancy transport region to about 2 × 10?3 where transport is probably by interstial motion at 360°C. For “Li3Bi” a practically constant value of nearly 10?1 Ω?1 cm?1 is found at 380°C. The parabolic tarnishing rate constant shows a sharp increase at higher lithium activities in “Li3Sb” whereas in “Li3Bi” it has a roughly linear dependence upon the logarithm of the lithium activity. The tarnishing process is about 2 orders of magnitude slower for “Li3Sb” than for “Li3Bi.” Because of the fast ionic transport in these mixed conducting materials, “Li3Sb” and “Li3Bi” may be called “fast electrodes.”  相似文献   

3.
Solid‐oxide Li+ electrolytes of a rechargeable cell are generally sensitive to moisture in the air as H+ exchanges for the mobile Li+ of the electrolyte and forms insulating surface phases at the electrolyte interfaces and in the grain boundaries of a polycrystalline membrane. These surface phases dominate the total interfacial resistance of a conventional rechargeable cell with a solid–electrolyte separator. We report a new perovskite Li+ solid electrolyte, Li0.38Sr0.44Ta0.7Hf0.3O2.95F0.05, with a lithium‐ion conductivity of σLi=4.8×10?4 S cm?1 at 25 °C that does not react with water having 3≤pH≤14. The solid electrolyte with a thin Li+‐conducting polymer on its surface to prevent reduction of Ta5+ is wet by metallic lithium and provides low‐impedance dendrite‐free plating/stripping of a lithium anode. It is also stable upon contact with a composite polymer cathode. With this solid electrolyte, we demonstrate excellent cycling performance of an all‐solid‐state Li/LiFePO4 cell, a Li‐S cell with a polymer‐gel cathode, and a supercapacitor.  相似文献   

4.
The sequential segregation of Sn and Sb to the surface of a Cu(111) single crystal was measured in the temperature range 400–1100 K by Auger electron spectroscopy. It was found that Sn with the higher diffusion coefficient first segregates to the surface and then is replaced by the slower‐segregating Sb. The results were fitted by a ternary segregation model yielding segregation energies (ΔGSn = 76.3 kJ mol?1, ΔGSb = 95.9 kJ mol?1), interaction parameters (ΩSnCu = 3.8 kJ mol?1, ΩSbCu = 16.2 kJ mol?1, ΩSnSb = ?5.3 kJ mol?1) and diffusion coefficients (D0(Sn) = 1.8 × 10?5 m2 s?1, ESn = 173 kJ mol?1, D0(Sb) = 6.0 × 10?5 m2 s?1, ESb = 205 kJ mol?1) for both species. The validity of the interaction coefficients and segregation energies was verified using the Guttman equations for equilibrium segregation in ternary systems. Copyright © 2003 John Wiley & Sons, Ltd.  相似文献   

5.
To reveal the interaction mechanism between lithium (Li) and silicon/graphene (Si/Gra) interface at the atomic scale, it was calculated that the energy band structure, density of states, charge transfer, radial distribution function and Li diffusion coefficient based on the first principles. The results indicated that the volume expansion of Si was effectively limited by the Si/Gra interface during Li insertion. There appeared the interface effect of Si/Gra on the combination of Li and Si atoms, according to the longer Li-C (2.9 Å) and the larger electron cloud near the Li atom at the Si/Gra interface. The better diffusion channel for Li atoms was constructed at the Si/Gra interface, due to the lower diffusion energy barrier (0.42–0.44 eV) and higher diffusion coefficient (DLi = 0.784 × 10−4 cm2/s) for Li+ diffusion.  相似文献   

6.
The need to improve electrodes and Li‐ion conducting materials for rechargeable all‐solid‐state batteries has drawn enhanced attention to the investigation of lithium‐rich compounds. The study of the ternary system Li‐Si‐P revealed a series of new compounds, two of which, Li8SiP4 and Li2SiP2, are presented. Both phases represent members of a new family of Li ion conductors that display Li ion conductivity in the range from 1.15(7)×10?6 Scm?1 at 0 °C to 1.2(2)×10?4 Scm?1 at 75 °C (Li8SiP4) and from 6.1(7)×10?8 Scm?1 at 0 °C to 6(1)×10?6 Scm?1 at 75 °C (Li2SiP2), as determined by impedance measurements. Temperature‐dependent solid‐state 7Li NMR spectroscopy revealed low activation energies of about 36 kJ mol?1 for Li8SiP4 and about 47 kJ mol?1 for Li2SiP2. Both compounds were structurally characterized by X‐ray diffraction analysis (single crystal and powder methods) and by 7Li, 29Si, and 31P MAS NMR spectroscopy. Both phases consist of tetrahedral SiP4 anions and Li counterions. Li8SiP4 contains isolated SiP4 units surrounded by Li atoms, while Li2SiP2 comprises a three‐dimensional network based on corner‐sharing SiP4 tetrahedra, with the Li ions located in cavities and channels.  相似文献   

7.
Novel Lithium Chloride Suzuki Phases, Li6MCl8 (M = Fe, Co, Ni) The hitherto unknown Suzuki phases Li6FeCl8, Li6CoCl8, and Li6NiCl8 ( cF 60) were prepared by fusing the binary chlorides. X-ray, DTA, and conductivity data as well as the infrared and Raman spectra are presented. The unit cell dimensions of the cubic (space group Fm3 m) halides are a = 1029.3, 1027.5, and 1023.5 pm, respectively. Li6FeCl8 and Li6CoCl8 undergo a reversible phase transition to disordered LiCl solid solutions at 275 and 355°C, respectively. The metastable nickel compound can only be prepared by quenching from about 560°C. The lithium chloride Suzuki phases are fast lithium ion conductors at elevated temperatures. The specific conductivities are 1.4 × 10?1, 1.5 × 10?1, and 6.9 × 10?2Ω?1 × cm?1 at 500°C, respectively. Whereas the i.r. spectra of the Suzuki phases only reveal a broad band, the Raman spectra exhibit the four group theoretically allowed modes as sharp scattering peaks, which are discussed in terms of the vibrational modes of this structure.  相似文献   

8.
An investigation is conducted on enhancing lithium-ion intercalation and conduction performance of transparent organo tantalum oxide (TaO y C z ) films, by addition of lithium via a fast co-synthesis onto 40 Ω/□ flexible polyethylene terephthalate/indium tin oxide substrates at the short exposed durations of 33–34 s, using an atmospheric pressure plasma jet (APPJ) at various mixed concentrations of tantalum ethoxide [Ta(OC2H5)5] and lithium tert-butoxide [(CH3)3COLi] precursors. Transparent organo-lithiated tantalum oxide (Li x TaO y C z ) films expose noteworthy Li+ ion intercalation and conduction performance for 200 cycles of reversible Li+ ion intercalation and deintercalation in a 1 M LiClO4-propylene carbonate electrolyte, by switching measurements with a potential sweep from ?1.25 to 1.25 V at a scan rate of 50 mV/s and a potential step at ?1.25 and 1.25 V, even after being bent 360° around a 2.5-cm diameter rod for 1000 cycles. The Li+ ionic diffusion coefficient and conductivity of 6.2?×?10?10 cm2/s and 6.0?×?10?11 S/cm for TaO y C z films are greatly progressed of up to 9.6?×?10?10 cm2/s and 7.8?×?10?9 S/cm for Li x TaO y C z films by co-synthesis with an APPJ.  相似文献   

9.
A method of electrochemical impedance spectroscopy was used to study the reversible lithium intercalation from nonaqueous electrolyte into tin films with the thickness of 0.1–1 μm. The impedance spectra of lithium-tin (Li x Sn) electrodes have a complicated shape depending on the electrode state and prehistory; they reflect the occurrence of several consecutive and parallel processes, including the lithium migration, diffusion, and accumulation. The formation of a solid-electrolyte layer on the surface at Li intercalation into Sn is observed. Equivalent circuits are proposed that adequately model the experimental data on the Li x Sn electrodes both freshly prepared and after prolonged cycling. Problems associated with the choice of equivalent circuits and determination of their parameters, the accuracy of the diffusion coefficient determination, the trends in the parameters’ variation with electrode potential (composition) are discussed.  相似文献   

10.
A cubic Li5La3Nb2O12 phase with a garnet framework was synthesized by the sol–gel process, in which lithium hydroxide, niobium oxide and acetic lanthanum were used as starting materials, while water was used as solvent. Pure garnet-like Li5La3Nb2O12 powders were obtained after heating the gel precursor at 700 °C for 6 h with 10 % excess lithium salt. The calcination temperature is nearly 250 °C lower than that by the solid state reaction. The phase transforms from cubic to tetragonal symmetry with loss of lithium at 717 °C, but the garnet framework remains stable to above 900 °C. A pellet annealed at 900 °C for 6 h had a room-temperature Li+-ion conductivity σLi (22 °C) = 1.0 × 10?5 S cm?1, a little higher than that attained by solid-state synthesis. The Li5La3Nb2O12 compound was chemically stable against two commonly used cathode materials, LiMn2O4 and LiCoO2, up to 900 °C and against metallic lithium.  相似文献   

11.
Carbon-coated Na3V2(PO4)3 (NVP) was prepared by a standard sol–gel procedure. The apparent diffusion coefficients of sodium ions in the rhombohedral NVP have been determined by different techniques such as galvanostatic intermittent titration technique (GITT) and cyclic voltammetry (CV). It was found that the apparent diffusion coefficients range from 6?×?10?13 cm2 s?1 to 2?×?10?15 cm2 s-1. These sodium ion apparent diffusion coefficients follow a similar trend as observed for lithium ions in the closely related monoclinic modification of Li3V2(PO4)3, demonstrating a minimum at the potential where the ion extraction/insertion occurs.  相似文献   

12.
Layered, lithium-rich Li[Li0.2Co0.3Mn0.5]O2 cathode material is synthesized by reactions under autogenic pressure at elevated temperature (RAPET) method, and its electrochemical behavior is studied in 2?M Li2SO4 aqueous solution and compared with that in a non-aqueous electrolyte. In cyclic voltammetry (CV), Li[Li0.2Co0.3Mn0.5]O2 electrode exhibits a pair of reversible redox peaks corresponding to lithium ion intercalation and deintercalation at the safe potential window without causing the electrolysis of water. CV experiments at various scan rates revealed a linear relationship between the peak current and the square root of scan rate for all peak pairs, indicating that the lithium ion intercalation–deintercalation processes are diffusion controlled. The corresponding diffusion coefficients are found to be in the order of 10?8?cm2?s?1. A typical cell employing Li[Li0.2Co0.3Mn0.5]O2 as cathode and LiTi2(PO4)3 as anode in 2?M Li2SO4 solution delivers a discharge capacity of 90?mA?h g?1. Electrochemical impedance spectral data measured at various discharge potentials are analyzed to determine the kinetic parameters which characterize intercalation–deintercalation of lithium ions in Li[Li0.2Co0.3Mn0.5]O2 from 2?M Li2SO4 aqueous electrolyte.  相似文献   

13.
Li5SiN3 crystals are synthesized by direct reaction between Li3N and Si3N4 with the molar ratio Li3N/Si3N4 of 10:1. Reaction is performed at 1073 K for 1 h under a nitrogen atmosphere of 700 Torr. The lattice constant determined by the X-ray powder diffraction method is 4.718 Å. Four broad Raman peaks are observed at 196, 286, 580, and 750 cm?1. By analogy with LiMgN, the broad peak at 580 cm?1 with a half width of 140 cm?1 is attributed to homogenously random distribution of Li and Si atoms. The band gap of Li5SiN3 is found to be a direct gap of about 2.5 eV by optical absorption and photoacoustic spectroscopy methods. Comparison with the conventional cathode materials for lithium ion batteries, this gap value is close to d-d transition energy of Mn in LiMn2O4 (1.63 eV or 2.00 eV) and that of Co in LiCoO2 (2.1 eV), suggesting that Li5SiN3 is a possible cathode material. The 5 × 5 mm2-sized lithium secondary battery of Li5SiN3 cathode/propylene carbonate + LiClO4 electrolyte/Li anode structure shows a discharge capacity of 2.4 μAh cm?2 for a discharge current of 1.0 μA.  相似文献   

14.
The study of a novel catalyst containing LiCl and SnCl2 (LiSn/AC) for acetylene hydrochlorination has been reported in this paper. Furthermore, the performance of both high activity (98.3%) and selectivity (>98.0%) are achieved by LiSn/AC catalysts under the reaction temperature of 200 °C and C2H2 hourly space velocity of 30 h?1. The structural characteristics of the Sn based catalysts were deeply researched via BET, XRD, TEM, TPR, C2H2-TPD, XPS and TG techniques. According to these characteristic results, we proposed that the presence of Sn2+ exhibited better activity and stability than that of Sn4+ in Sn based catalysts. Additionally, LiCl additives not only can restrain the oxidation of Sn2+ and the loss of Sn4+ in fresh Sn based catalysts but also make the Snδ+ (δ = 2,4) species dispersed well on the surface of support. Therefore, the adsorption capacity of C2H2 and HCl was enhanced in LiSn/AC, which exhibited the better catalytic performance than that of Sn based catalyst.  相似文献   

15.
Electrolytes with high lithium-ion conductivity, better mechanical strength and large electrochemical window are essential for the realization of high-energy density lithium batteries. Polymer electrolytes are gaining interest due to their inherent flexibility and nonflammability over conventional liquid electrolytes. In this work, lithium garnet composite polymer electrolyte membrane (GCPEM) consisting of large molecular weight (Wavg ~?5?×?106) polyethylene oxide (PEO) complexed with lithium perchlorate (LiClO4) and lithium garnet oxide Li6.28Al0.24La3Zr2O12 (Al-LLZO) is prepared by solution-casting method. Significant improvement in Li+ conductivity for Al-LLZO containing GCPEM is observed compared with the Al-LLZO free polymer membrane. Maximized room temperature (30 °C) Li+ conductivity of 4.40?×?10?4 S cm?1 and wide electrochemical window (4.5 V) is observed for PEO8/LiClO4?+?20 wt% Al-LLZO (GCPEM-20) membrane. The fabricated cell with LiCoO2 as cathode, metallic lithium as anode and GCPEM-20 as electrolyte membrane delivers an initial charge/discharge capacity of 146 mAh g?1/142 mAh g?1 at 25 °C with 0.06 C-rate.  相似文献   

16.
Sn-doped Li-rich layered oxides of Li1.2Mn0.54-x Ni0.13Co0.13Sn x O2 have been synthesized via a sol-gel method, and their microstructure and electrochemical performance have been studied. The addition of Sn4+ ions has no distinct influence on the crystal structure of the materials. After doped with an appropriate amount of Sn4+, the electrochemical performance of Li1.2Mn0.54-x Ni0.13Co0.13Sn x O2 cathode materials is significantly enhanced. The optimal electrochemical performance is obtained at x = 0.01. The Li1.2Mn0.53Ni0.13Co0.13Sn0.01O2 electrode delivers a high initial discharge capacity of 268.9 mAh g?1 with an initial coulombic efficiency of 76.5% and a reversible capacity of 199.8 mAh g?1 at 0.1 C with capacity retention of 75.2% after 100 cycles. In addition, the Li1.2Mn0.53Ni0.13Co0.13Sn0.01O2 electrode exhibits the superior rate capability with discharge capacities of 239.8, 198.6, 164.4, 133.4, and 88.8 mAh g?1 at 0.2, 0.5, 1, 2, and 5 C, respectively, which are much higher than those of Li1.2Mn0.54Ni0.13Co0.13O2 (196.2, 153.5, 117.5, 92.7, and 43.8 mAh g?1 at 0.2, 0.5, 1, 2, and 5 C, respectively). The substitution of Sn4+ for Mn4+ enlarges the Li+ diffusion channels due to its larger ionic radius compared to Mn4+ and enhances the structural stability of Li-rich oxides, leading to the improved electrochemical performance in the Sn-doped Li1.2Mn0.54Ni0.13Co0.13O2 cathode materials.  相似文献   

17.
The glass–ceramic electrolytes of (100?x)(0.8Li2S·0.2P2S5xLiI (in mole percent; x?=?0, 2, 5, 10, 15, 20, and 30) were prepared by mechanical milling and subsequent heat treatment. Crystalline phases analogous to the thio-LISICON region II or III in the Li2S–GeS2–P2S5 system were precipitated. The thio-LISICON III analog phase was mainly precipitated at the composition x?=?0, and the thio-LISICON II analog phase was precipitated in the composition range from x?=?2 to 15. The X-ray diffraction peaks of the thio-LISICON II analog phase shifted to the lower diffraction angle side with increasing the LiI content. High conductivities above 2?×?10?3?S?cm?1 at room temperature were observed in the glass–ceramics at the wide composition range from x?=?2 to 15. The glass–ceramic electrolyte at x?=?5 with the highest conductivity of 2.7?×?10?3?S?cm?1 showed a wide electrochemical window of about 10 V. The addition of LiI to the 80Li2S·20P2S5 (in mole percent) glass was effective in crystallizing the thio-LISICON II analog phase with high conductivity from the glass.  相似文献   

18.
The series of RE5Li2Sn7 (RE = Ce–Sm) compounds were synthesized by high‐temperature reactions and structurally characterized by single‐crystal X‐ray diffraction. The compounds are pentacerium dilithium heptastannide, Ce5Li1.97Sn7.03, pentapreseodymium dilithium heptastannide, Pr5Li1.98Sn7.02, pentaneodymium dilithium heptastannide, Nd5Li1.99Sn7.01, and pentasamarium dilithium heptastannide, Sm5Li2Sn7. All five compounds crystallize in the chiral orthorhombic space group P212121 (No. 19), which is relatively uncommon among intermetallic phases. The structure belongs to the Ce5Li2Sn7 structure type (Pearson symbol oP56), with 14 unique atoms in the asymmetric unit. Minor compositional variations exist, due to the mixed occupancy of Li and Sn atoms at one of the Li sites. The small occupational disorder is most evident for RE5Li2−xSn7+x (RE = Ce, Pr; x≃ 0.03), while the structure of Nd5Li2Sn7 and Sm5Li2Sn7 show no apparent disorder.  相似文献   

19.
The galvanostatic intermittent titration technique is used to study lithium transport in the LiM y Mn2 − y O4 compounds with a spinel structure intended for application as cathodic materials in lithium-ion and lithium-polymer batteries. Equilibrium intercalation isotherms of the Li x Mn2O4 and Li x Mn1.95Cr0.05O4 compounds and also their diffusion characteristics are determined at 25°C as dependent on lithium content x, 0 < x < 1. The diffusion coefficient of lithium varies in a complex way in the range of 10−10 to 10−12 cm2/s under variation of the electrode composition.  相似文献   

20.
《Analytical letters》2012,45(17-18):1371-1380
Abstract

1,4,7,10-Tetraoxacyclododecane (12-crown-4) (I) and its lithium complex (II) are used as neutral carriers for lithium ion in polyvinylchloride membrane ion selective electrodes. The lithium response varies with concentration, being near Mernstian at low (10?5-10?4 M) concentrations and sub-Nernstian (24-28 aV) at higher concentrations (10?3 M). The selectivity coefficients KLi Pot M for II are: Na+ (0.12), K+ (0.66), Cs+ (0.15), Mg2+ (1.6 × 10?4), Ca2+ (3.1 × 10?4), Ba2+ (9.5 × 10?7), NH+ 4 (9.0 × 10?2), H+ (2.2).  相似文献   

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