XPS and ionic conductivity studies on Li1.3Al0.15Y0.15Ti1.7(PO4)3 ceramics

Li_1.3Al_0.15Y_0.15Ti_1.7(PO₄)₃ compound was synthesized by solid-state reaction, and ceramics were sintered. The surfaces of the ceramics were investigated by scanning electron microscopy and X-ray photoelectron spectroscopy. Li_1.3Al_0.15Y_0.15Ti_1.7(PO₄)₃ samples were tested in solid galvanic cells Ag|O₂+CO₂|Li₂CO₃|Li_1.3Al_0.15Y_0.15Ti_1.7(PO₄)₃|LiMnO₂+Mn₂O₃|O₂|Ag. The electromotive force measurements of this cell indicated that investigated samples are practically pure Li-ion conductors. Impedance spectroscopy studies have been performed in the frequency range 10^?2–3·10⁹ Hz and temperatures from ?57 °C to 334 °C. Three dispersion regions related to Li⁺ ionic transport in bulk, grain boundaries of the ceramics and to polarization of electrodes have been found. Total conductivity changes according to Arrhenius law in the studied temperature range, but an anomalous behavior was observed for the bulk conductivity of the ceramics.     

锌掺杂固态电解质材料磷酸钛铝锂的制备及第一性原理研究

高安全性的固体锂离子电池是目前研究的热点之一,固态电解质是研究全固态电池的关键.磷酸钛铝锂固体电解质(LATP)具有良好的发展空间,因此采用高温固相法,制备锌掺杂LATP(LAZTP)固体电解质,通过XRD、SEM分析对比其物象和形貌特征,并对这两种材料压片进行阻抗分析,研究材料的电化学性能.基于密度泛函理论的第一性原理,研究LAZTP的能带结构和态密度与材料电化学性能的关系.结果表明:所掺杂锌的LATP材料,在球磨工艺下,与LATP相比衍射峰尖锐,材料结晶度良好,都为R-3C结构,LAZTP微观尺度下材料颗粒清晰,呈块状,孔隙均匀致密度较好,离子电导率相比较高,为1.9×10^-3S/cm,而制作的LATP的电导率为4.02x10^-4 S/cm,掺杂后的电导率明显高出一个数量级.计算得出的LATP能带带隙为0.163 eV和LAZTP能带带隙为0.05 eV,分态密度中Ti-s、Li-s、Al-s峰值尖锐,变化明显,表明掺杂锌后,材料明显提高了导电率和结构稳定性.     

Spin-alignment echo NMR: probing Li+ hopping motion in the solid electrolyte Li7La3Zr2O12 with garnet-type tetragonal structure

(7)Li spin-alignment echo (SAE) nuclear magnetic resonance (NMR) spectroscopy has been used to measure single-spin hopping correlation functions of polycrystalline Li(7)La(3)Zr(2)O(12). Damping of the echo amplitude S(2)(t(m),t(p)), recorded at variable mixing time t(m) but fixed preparation time t(p), turns out to be solely controlled by slow Li jump processes taking place in the garnet-like structure. The decay rates τ(SAE)(-1) directly obtained by parametrizing the curves S(2)(t(m),t(p)) with stretched exponential functions show Arrhenius behaviour pointing to an activation energy of approximately 0.5 eV. This value, probed by employing an atomic-scale NMR method, is in very good agreement with that deduced from impedance spectroscopy used to measure macroscopic Li transport parameters. Most likely, the two methods are sensitive to the same hopping correlation function although Li dynamics are probed in a quite different manner.     

Preparation of Li1.5Al0.5Ti1.5(PO4)3 solid electrolyte via a co-precipitation method

The co-precipitation method can make the materials react uniformly at molecular level and has the advantages of lower polycrystalline synthesized temperature and shorter sintering time. Therefore, it is expected that the mass production of Li_1.5Al_0.5Ti_1.5(PO₄)₃ (LATP) solid electrolyte would be possible by application of the co-precipitation method for LATP preparation. In this study, an application of the co-precipitation method for a preparation of LATP solid electrolyte is attempted. Crystallized LATP powder is obtained by heating precipitant containing Li, Al, Ti, and PO₄ at 800 °C for 30 min. The LATP bulk sintered pellet is successfully prepared using the crystallized LATP powder by calcinating at 1,050 °C. The cross-sectional SEM images show that many crystal grains exist, and the grains are in good contact with each other, i.e., there is no void space. All diffraction peaks of the pellet are attributed to LATP in XRD pattern. The sintered pellet is obtained by calcinating at 1,050 °C, which is more than 150 °C lower than that of conventional method. The LATP solid electrolyte shows a good conductivity which is 1.4?×?10^?3 S cm^?1 for bulk and 1.5?×?10^?4 S cm^?1 for total conductivities, respectively.     

Distortion of the Ligand Environment of Gd3+ and Eu2+ Ions in Garnets: Y3Al5O12, Lu3Al5O12, and Y3Ga5O12

Physics of the Solid State - Using experimental second-rank parameters of the spin Hamiltonian of the rhombic centers Gd3+ and Eu2+ in three garnets and the superposition approximation...     

Enhanced superhyperfine interaction on Ru3+ in Tm3Al5O12 and on Ru3+ and Yb3+ in Tm3Ga5O12

Measurements of the enhanced superhyperfine interaction linking the electron spin of an impurity EPR ion and the nuclear moments of Van Vleck host lattice ions are reported for Ru³⁺ in Tm₃Al₅O₁₂ and for Ru³⁺ and Yb³⁺ in Tm₃Ga₅O₁₂. The Ru³⁺ results appear to be the first reported where this interaction is large enough to give rise to a well resolved superhyperfine structure. For Yb³⁺ the observed temperature dependent line narrowing evidences the role of Tm spin fluctuations.     

The ionic conductivity of Li6BaLa2M2O12 with coexisting Nb and Ta on the M sites

In a view to balancing cost and lithium ion conductivity, Li₆BaLa₂Nb _x Ta_2???x O₁₂ (x?=?0–2) was prepared by solid-state reaction, and its corresponding AC impedances were tested at temperatures ranging from 20 to 250 °C in air. Li₆BaLa₂Ta₂O₁₂ exhibits the highest conductivity, 8.77?×?10^?6?S/cm, and the second highest is Li₆BaLa₂Nb₂O₁₂ with 6.69?×?10^?6?S/cm. Partial replacement of Ta with Nb cannot bestow the advantages of cost saving or the enhancement of lithium ion conductivity. X-ray diffraction patterns revealed a gradual change as an increasing amount of Nb replaces Ta in Li₆BaLa₂Nb _x Ta_2???x O₁₂ (x?=?0–2), and it is thought that the trending of Nb and Ta to rest on the crystallographic planes is different.     

An anomalous enhancement in the electrical conductivity of Li2O : B2O3 : Al2O3 glasses

The study of electrical conductivity of 27.5 Li₂O : (72.5 − x) B₂O₃ : x Al₂O₃ glass samples has been carried out. It has been observed that the conductivity exhibits Arrhenius behavior for all samples up to glass transition temperature T_g. Beyond T_g, an anomalous enhancement followed by decrease in conductivity has been observed. The results have been explained by dividing the temperature range into two regions. In region-I, it has been observed that the conductivity variation exhibits a maximum at 2.5 mol% Al₂O₃, which has been explained on the basis of Mixed Glass Former Effect (MGFE). An anomalous enhancement in the conductivity observed in region-II has been attributed to the nucleation in the glass. The subsequent decrease in the conductivity has been attributed to the crystallization of the glass samples.     

Preparation and structural instability of the 0.1BiFeO3-0.9Bi4Ti3O12 system

The solid solution of 0.1BiFeO₃-0.9Bi₄Ti₃O₁₂ (BF-BT) with bismuth-layered perovskite structure was obtained by conventional solid-state reaction. The lattice instability of BF-BT has been investigated by variable-temperature Raman scattering and X-ray diffraction. The results showed that there was a ferroelectric phase transition in the 450∼550 °C region in terms of the evolution of temperature dependence of Raman scattering frequencies. Some changes at about 530 °C in the XRD lines, the lattice parameters (a, b and c) as well as the orthorhombic distortion b/a have been detected in the high temperature X-ray diffraction, which can be interpreted by a phase transition and it is in good agreement with the results of high temperature Raman scattering. PACS 77.80.Bh; 61.10.Eq; 63.20.Dj     

Y3Al5O12:Ce3+的余辉和热释光特性

高温固相法合成了Ce3+掺杂的Y3Al5O12(YAG)样品,研究了样品的结构、光致发光和热释发光性质.X射线衍射分析结果表明合成样品为YAG纯相,稀土离子的少量掺杂不改变基质YAG的结构.荧光光谱测试表明在高温空气气氛下Y2.95Al5O12:Ce4+0.05制备过程中存在Ce4+的自还原现象,一部分Ce4+被自还原为Ce3+,导致531nm黄光宽带发射.弱还原气氛下制备的Y2.95Al5O12:Ce3+0.05在紫外光照射后具有黄色长余辉,余辉时间长达35 min.热释光测试表明在Ce3+掺杂的YAG样品中存在热释发光,在弱还原气氛下制备的样品Y2.95Al5O12:Ce3+0.05的热释光随温度变化曲线上有112℃和256℃两个明显的热释光峰;而在空气气氛下制备的样品Y2.95Al5O12:Ce4+0.05的热释光随温度变化曲线上只有128℃一个明显的热释光峰.通过对比研究,热释发光主要来源于YAG基质中缺陷能级所陷俘的Ce3+.