Ionic transport in the lithium nitride bromides,Li6NBr3 and Li1 3N4Br

The ionic and electronic conductivities of the lithium nitride bromides Li₆NBr₃ and Li_{1 3}N₄Br have been studied in the temperature range from 50 to 220°C and 120 to 450°C, respectively. Both compounds are practically pure lithium ion conductors with negligible electronic contribution. Li₆NBr₃ has an ionic conductivity Ω of 2 × 10^-6Ω^-1cm^-1 at 100°C and an activation enthalpy for σT of 0.46 eV. Li_{1 3}N₄Br shows a phase transition at about 230°C. The activation enthalpy for σT is 0.73 eV below and 0.47 eV above this temperature. The conductivities at 150 and 300°C were found to be 3.5 × 10^-6 Ω^-1cm^-1 and 1.4 × 10^-3Ω^-1cm^-1, respectively. The crystal structure is hexagonal at room temperature with $\text{a = 7.415 (1)}\text{A}\text{?}$ and $\text{c = 3.865 (1)}\text{A}\text{?}$.     

Li4SiO4-Li3VO4赝二元系和Li4GeO4-Li4SiO4-Li3VO4赝三元系中新的锂离子导体

本文在室温到300℃的温度范围内研究了Li₄SiO₄-Li₃VO₄和Li₄GeO₄-Li₄SiO₄-Li₃VO₄体系中的离子导电性,发现γ_II相固溶体Li_3+xV_1-xSi_xO₄是好的锂离子导体。所研究的成分中Li_3.3V_0.7Si_0.3O₄的离子电导率最高,室温下为1×10^-5Ω^-1·cm^-1,在42—192℃的电导激活能为0.36eV,电子电导率可以忽略,因而这是迄今所发现的最好的锂离子导体之一。粗略确定了Li₄GeO₄-Li₄SiO₄-Li₃VO₄三元系中电导率高的范围,发现在Li_3.5V_0.5Ge_0.5O₄中Si部分取代Ge可以使电导率进一步提高,Li_3.5V_0.5Ge_0.4Si_0.1O₄的室温电导率可达1.3×10^-5Ω^-1·cm^-1,电导激活能为0.40eV。 关键词：     

LiF-LiCl-B2O3系统非晶态快离子导体结构的研究

本文通过对¹¹B核磁共振(¹¹B-NMR)、红外光谱等实验方法,研究了LiF-LiCl-B₂O₃三元系统玻璃的结构和离子导电性,着重于F^-离子在玻璃网络中所起的作用,以及F^-,Cl^-和Li⁺离子对导电率的影响。LiF-LiCl-B₂O₃三元系统玻璃,随LiF含量的增加,B由三角体向四面体变化,从而F^-离子进入网络,使玻璃结构由[B₂O₃]三角体层状结构向三维空间延展,形成了含有[BO₃F]基团的三维空间网络,Cl^-离子以游离的离子存在于网络中,起着松散网络的作用,对提高电导率有利,而Li⁺离子作为传导离子,对电导率的贡献是主要的。本系统玻璃的电导率是随LiF,LiCl含量的增加而增大,在300℃时测得电导率σ=6.12×10^-4Ω^-1·cm^-1。 关键词：     

LISICON(锗酸锌锂)单晶的Li+离子电导

本文研究了Lisicon(锗酸锌锂)单晶的Li⁺离子电导率。发现各结晶学方向电导率之间的关系为σ_b≤σ_a≤σ_c≤σ_[110],但各向异性不强。晶体中Li含量对电导率有明显的影响,当Li/Zn比率由6.7变到9.2时,300℃a方向电导率由4.3×10^-2Ω^-1·cm^-1增加到1.25×10^-1Ω^-1·cm^-1,logσT对1/T的曲线显示出三个转变点,分别在～80℃,～140℃和～300℃。电导的激活能分别为0.50—0.58eV(25—80℃),0.92eV(～80—140℃),0.64eV(～140—300℃)和0.36eV(>300℃),极化实验表明单晶的电子电导可以忽略。 关键词：     

Ionic conductivity of lithium nitride doped with hydrogen

Lithium ionic conductivity of Li₃N single crystals is reported for temperatures from 120 K to 350 K. The intrinsic ionic conductivity is rather small (< 10^?6 Ω^?1 cm^?1 at 300 K) and shows no strong anisotropy. The activation energy is near 0,6 eV. It is shown that hydrogen is the critical impurity in the crystals grown and studied at this laboratory. The relative impurity concentration is determined from infrared transmission measurements near 3130 cm^?1. An estimate for absolute values is obtained from dielectric studies. Increases in ionic conductivity with hydrogen doping by a factor 5000 are reported for E⊥c but no significant effects are found for E6c. The proposed defect is an impurity-vacancy complex consisting of an NH^?? and a lithium vacancy.     

多晶Li3+xV1-xTxO4(T=Ge,Si)离子导电性能的改善

本文用阻抗谱方法研究了Li_3+xV_1-xT_xO₄(T=Si,Ge)多晶的离子导电性,发现一些工艺条件如成型压强、烧结时间和烧结程序对电导率有很大影响。注意分析了这些影响的物理起因。最佳工艺条件是:在大约8t/cm²压强下成型样品。在1000℃连续烧结5至6天,烧结过程中,应尽量避免温度波动。在此条件下制备的Li_3.5V_0.5Ge_0.5关键词：     

50 MeV Li3+ ion irradiation effect on structural, electrical, and dielectric properties of PVA-based nanocomposite polymer electrolytes

Nanocomposite polymer electrolyte thin films of polyvinyl alcohol (PVA)-orthophosphoric acid (H₃PO₄)-Al₂O₃ have been prepared by solution cast technique. Films are irradiated with 50 MeV Li³⁺ ions having four different fluences viz. 5?×?10¹⁰, 1?×?10¹¹, 5?×?10¹¹, and 1?×?10¹² ions/cm². The effect of irradiation on polymeric samples has been studied and characterized. X-ray diffraction spectra reveal that percent degree of crystallinity of samples decrease with ion fluences. Glass transition and melting temperatures have been also decreased as observed in differential scanning calorimetry. A possible complexation/interaction has been shown by Fourier transform infrared spectroscopy. Temperature-dependent ionic conductivity shows an Arrhenius behavior before and after glass transition temperature. It is observed that ionic conductivity increases with ion fluences and after a critical fluence, it starts to decrease. Maximum ionic conductivity of ～2.3?×?10^?5 S/cm owing to minimum activation energy of ～0.012 eV has been observed for irradiated electrolyte sample at fluence of 5?×?10¹¹ ions/cm². The dielectric constant and dielectric loss also increase with ion fluences while they decrease with frequency. Transference number of ions shows that the samples are of purely ionic in nature before and after ion irradiation.     

Li2Mo2O6多晶材料的结构与电性能的研究

本文用固相反应烧结制备出Li₂Mo₂O₆多晶材料。经X射线分析、红外光谱和电子顺磁共振谱(EPR)的研究,确定了它的结构是Li₂Mo₂O₄和MoO₂两个晶相组成的烧结体。钼离子以四价状态存在于MoO₂晶相结构中。采用交流阻抗谱分析了晶界与温度变化的相关性。测得了样品的ln(σ_总T)-1/T 曲线是由两段直线和一段曲线所组成;总电导率化能σ_27℃=1.36×10^-3(Ω·cm)^-1,σ_115℃=1.49×10^-3(Ω·cm)^-1,σ_300℃=9.71×10^-3(Ω·cm)^-1,σ_370℃=2.42×10^-3(Ω·cm)^-1;电导活化能E₁=0.043eV,E₂=0.235eV,E_平均=0.76eV。采用维格纳极化电池法测得电子电导率σ_e,σ_e27℃=2.240×10^-5(Ω·cm)^-1,σ_e300℃=4.476×10^-3(Ω·cm)^-1。实验证明,室温下材料为固体电解质,300℃附近为良好的离子与电子混合导体。 关键词：     

插层化合物Li1+xV3O8的合成及其物理性能的初步研究

本文成功地合成了插层化合物Li_1+xV₃O₈,并用X射线粉末衍射和等离子体发射光谱元素定量分析进行了鉴定。同时进行了NMR研究。在298—400K之间观察到了锂离子的运动致窄效应,并以此求得它的离子运动激活能为0.18eV。还测得该材料的室温电导率为10^-3Ω^-1·cm^-1数量级。 关键词：     

Lithium ion conduction in lithium metaphosphate based systems

A comparative investigation on Li⁺ ion transport has been carried out in various phases of lithium metaphosphate such as (i) crystalline LiPO₃, (ii) glassy form as mol % 50Li₂O-50P₂O₅, synthesized by melt-quenching process, (iii) single phase glass-ceramic LiPO₃ obtained through controlled heat treatment of mol % 50Li₂O-50P₂O₅ and (iv) newly identified polymer-metal salt complex (PEO)₆: LiPO₃. All of the above materials have been characterized through XRD, DSC, optical microscopy and impedance spectroscopy techniques. The Li⁺ ions, migrating with an activation energy value of 1.4 eV through “interstitial mechanism” in polycrystalline LiPO₃, exhibited a dc conductivity value of 2.5×10^-8 Scm^-1 at 280 °C. The above conductivity value was enhanced by four orders of magnitude in Li₂O-P₂O₅ glass, with an activation energy value of 0.72 eV. The glass subjected to controlled heat treatment devitrified into single phase glass-ceramic, as revealed by XRD and optical microscopy studies. The glass-ceramic exhibited better conduction characteristics compared to polycrystalline LiPO₃. Polycrystalline LiPO₃, complexed with polymer PEO has exhibited a conductivity value of 3.1×10^-7 Scm^-1 at 78 °C with activation energies of 0.21 and 0.88 eV for Li⁺ ion migration above and below the softening point of the polymer, respectively. PACS 66.10.Ed; 71.55.Jv; 81.30.Hd; 82.45.Gj; 82.45.Wx     

Protonic conductivity of β″ and ion-rich β-alumina. II: Ammonium compounds

The conductivity and thermal stability of NH⁺₄, H⁺(H₂O)_nβ″ and ion-rich β-alumina single crystals have been measured by the complex impedance method in the 25–700°C temperature range. Both structures have similar properties, but ion-rich β-alumina shows a higher stability and a lower activation energy (β: 0.18 eV, β″ 0.24 eV below 400°C and 250°C respectively). The room temperature conductivity is about 3×10^-5ω^-1cm^-1. The conducting properties and mechanisms are discussed and compared to other protonic or ionic conductors.     

Electrical conductivity and dielectric relaxation behavior of AgFeP2O7 compound

In the present study, AgFeP₂O₇ was prepared by a solid-state reaction method. Rietveld refinement of the X-ray diffraction pattern suggests the formation of the single phase desired compound with monoclinic structure at room temperature. Not only were the impedance spectroscopy measurements of our compound carried out from 209 Hz to 5 MHz over the temperature range of 553 K–698 K but its AC conductivity as well as the dielectric relaxation were evaluated. Impedance measurements show AgFeP₂O₇ an ionic conductor being the conductivity 1.04?×?10^–?5(Ω^–?1cm^–?1) at 573 K. The conductivity and modulus formalisms provide nearly the same activation energies for electrical relaxation of mobile ions revealing that transport properties in this material appear to be due to an ionic hopping mechanism dominated by the motion of the Ag⁺ ions along tunnels presented in the structure of the investigated material.     

Li2Mo2-xWxO6多晶材料的结构、电学性能与导电机理的研究

本文采用还原气氛制备导电性能优良的多晶多相陶瓷材料Li₂Mo_2-xW_xO₆(x=0,0.1,0.3),采用粉末X射线衍射分析、特征X射线能谱分析、红外光谱分析和电子自旋共振波谱分析等现代测试手段,得到样品的物相结构为Li₂Mo_1-xW_xO₄和MoO₂两相组成。W的掺入主要取代Mo进入Li₂ 关键词：     

The mixed conductor properties of AgCrS2

A reinvestigation of the mixed conductivity of AgCrS₂ shows that the ionic conductivity increases from 3 × 10^-5 (Ω-cm)^-1 at 25°C to 0.3 (Ω-cm)^-1 just above the order-disorder transition temperature of 400°C, whereas the electronic part is much smaller. Structural evidence is presented, that a fraction of the silver ions occupy off-site octahedral positions in the disordered phase.     

AlF3-K2NbOF5系统非晶态材料离子导体的结构与电性能

本文研究了AlF₃-K₂NbOF₅系列玻璃导电性。通过对AlF₃-K₂NbOF₅系列玻璃的Raman光谱研究,初步确认了玻璃的结构。根据结构随组成的变化情况,进一步讨论了玻璃的电导率。AlF₃-K₂NbOF₅二元系玻璃,当AlF₃的含量在21—29mol％范围内时,Al^{3+关键词：}     

Vibrational,electrical, and structural properties of PVDF–LiBOB solid polymer electrolyte with high electrochemical potential window

Polyvinylidene difluoride (PVDF)–lithium bis(oxalato)borate (LiBOB) solid polymer electrolytes (SPEs) have been prepared by solution casting. The highest ionic conductivity achieved is 3.4610^?3 S cm^?1. Electrochemical potential window of the SPEs is found around 4.7 V. Interaction between PVDF and LiBOB is studied systematically. The changes of C–C, CF₂, and CH₂ vibration modes with an emerging shoulder are analyzed. At higher salt content, this shoulder becomes more prominent peak at the expense of CF₂ vibration mode. This suggests the possible Li⁺?F coordination. Deconvolution of IR spectra region from 1750 to 1850 cm^?1 has been carried out to estimate the relative percentage of free ions and contact ions. The finding is in good agreement with conductivity and XRD results. When more salt is present, the number of free ions percentage increases and the Full width at half-maximum (FWHM) of (110) plane is broadening. The Li⁺?F interaction breaks the folding patterns of polymer chain and enhances amorphousness domain.     

Characterization and electrical behavior of new lithium chalcoborate thin films

Thin films obtained with glasses of the B₂S₃Li₂S and B₂S₃Li₂SLiI systems, using a vacuum evaporation technique have been investigated. In each system, amorphous thin films and starting glasses have the same composition and similar conductivities, about 10^?4 and 10^?3Ω^?1cm^?1 respectively at 25°C. The deposition rate was in both cases 140 Å s^?1. However, a thermal treatment at 90°C of the thin films containing lithium iodide enhances the conductivity by a factor of 10 and leads to lower activation energy (0.18 eV). This behavior has been identified as a Phipps effect and can be attributed to a quick ion diffusion along thin film - substrate interface. This interfacial region was found to show unique conduction properties including a very low Li⁺ migration enthalpy.     

Quasi-elastic scattering due to fast oxygen diffuson in yttria stabilized zirconia

Evidence for fast oxygen diffusion at high temperatures in single crystal ZrO₂ containing 12 mol % Y₂O₃ is presented from quasi-elastic light scattering data. Lattice vacancies are responsible for the enhanced ionic diffusion and the structural disorder. In the temperature range investigated we estimate the barrier activation energy for the jumping of oxygen vacancies to be 0.25 eV. At 1500°K the jump time is ～ 4 × 10^?12 sec., the diffusion constant is ～ 3.26 × 10^?5 cm²/sec. and the conductivity is ～ 0.24 (Ωcm)^?1.     

Influence of the annealing technique on the properties of Li ion-conductive Li1.3Al0.3Ti1.7(PO4)3 films

Li_1.3Al_0.3Ti_1.7(PO₄)₃ films were comparatively prepared by rapid thermal annealing (RTA) and conventional furnace annealing(CFA). The phase identification and surface morphology of the prepared films were characterized by X-ray diffraction and scanning electron microscopy. The electrochemical window, ionic conductivity, activation energy, and electronic conductivity were conducted by cyclic voltammetry, electrochemical impedance spectroscopy, and four-probe technique. The results show that the films prepared by RTA and CFA are homogenous and crack-free. The film prepared by RTA shows smaller grains and is denser than the one prepared by CFA. The electrochemical windows of the two films are beyond 2.4 V. The ionic conductivities of the films prepared by RTA and CFA are 2.7?×?10^?6 S cm^?1 and 1.4?×?10^?6 S cm^?1, respectively. The activation energy of the film prepared by RTA is 0.431 eV, which is slightly smaller than the one prepared by CFA. The electronic conductivity of the two films is about 10^?10 S cm^?1.     

Cross sections for slow ion production and charge transfer in H+3(D+3)−H2(D2) collisions

Slow ion production cross sections for collisions of H⁺₃ and D⁺₃ ions with H₂ and D₂ have been measured at collision energies between 100 eV and 500 eV. The values vary from 2 × 10^-17 cm² to 6 × 10^-17 cm². The smaller cross sections for D₃ projectiles may be explained as an internal energy effect.