Effect of P2O5 on the Nonisothermal Sinter‐Crystallization Process of a Lithium Aluminum Silicate Glass

Dense (~98.5%), lithium aluminum silicate glass‐ceramics were obtained via the sinter‐crystallization of glass particle compacts at relatively low temperatures, that is, 790–875°C. The effect of P₂O₅ on the glass‐ceramics' sinter‐crystallization behavior was evaluated. We found that P₂O₅ does not modify the surface crystallization mechanism but instead delays the crystallization kinetics, which facilitates viscous flow sintering. Our glass‐ceramics had virgilite (Li_xAl_xSi_3‐xO₆; 0.5 < x < 1), a crystal size <1 μm, and a linear thermal expansion coefficient of 2.1 × 10^?6°C^?1 in the temperature range 40–500°C. The overall heat treatment to obtain these GCs was quite short, at ~25 min.     

Sol–gel synthesis and infrared radiation property of Li-substituted cordierite

The Mg_2?xAl_4+1/2xLi_1/2xSi₅O₁₈ (0.1≤x≤1) ceramics with the substitution of (Li_1/2Al_1/2)²⁺ for Mg²⁺ were synthesized by the sol–gel method. The characterization of the modified cordierite included X-ray diffraction, SEM, EDS and infrared radiation. The crystal structure of Mg₂Al₄Si₅O₁₈ with the substitution of (Li_1/2Al_1/2)²⁺ for Mg²⁺ changed and the amount of secondary phase increased with increasing the x value from 0.1 to 1. High infrared emissivity over 0.9 in the band of 8–14 μm at room temperature was obtained in Mg_2?xAl_4+1/2xLi_1/2xSi₅O₁₈ (x=0.1). The material based on cordierite with x=0.1 sintered at 1200 °C maintained a single phase, compact microstructure and good infrared emissivity with potential use in infrared heating.     

Structure and microwave dielectric properties of Li(Al1-xLix)SiO4-x ceramics

Li(Al_1-xLi_x)SiO_4-x (x = 0.005, 0.01, 0.015, and 0.02) ceramics were synthesized via a traditional solid phase reaction method with different sintering temperatures. To determine the positions occupied by Li⁺ in the lattice, the defect formation energies and total energies of various sites of LiAlSiO₄ (LAS) occupied by Li⁺ were examined, and the energy of LAS systems were calculated using density functional theory of first-principle with the CASTEP module. The results demonstrated that the Al-sites occupied by Li⁺ had the lowest formation energies and total energy, so Li ⁺ should substitute Al³⁺. The impacts of replacing Al³⁺ with Li⁺ on the bulk density, sintering properties, phase composition, microstructure, and microwave dielectric properties of Li(Al_1-xLi_x)SiO_4-x (0 = x ≤ 0.02) ceramics were thoroughly studied. With Li⁺-doping, the sintering temperature decreased from 1300 °C (x = 0) to 1175 °C (x = 0.02), while the Q × f and τ_f values of LAS ceramics significantly increased. The Li(Al_0.99Li_0.01)SiO_3.99 ceramic was fully sintered at 1250 °C for 10 h to obtain excellent microwave dielectric properties: ε_r = 3.49, Q × f = 51,358 GHz, and τ_f = ?51.48 × 10^?6 °C^?1.     

Ferroelectric properties of Li‐doped BaTiO3 ceramics

We prepared 3 kinds of Li⁺‐doped BaTiO₃ ceramics by the solid‐state reaction method: (i) (Ba_1?xLi_x)TiO_3?x/2 having A‐site Li⁺, (ii) Ba(Ti_1?xLi_x)O_3?3x/2 having B‐site Li⁺, and (iii) x/2 Li₂CO₃+BaTiO₃ mixed one, for which we investigated the stable site of Li. The density of all prepared ceramics is above 95%. The results show that the lattice structure, the grain size, and the electric properties of Li⁺‐doped BaTiO₃ ceramics are dependent on Li⁺ site. According to the increase in Li content, the cell volume of Ba_1?xLi_xTiO_3?x/2 decreases, but that of BaTi_1?xLi_xO_3?3x/2 increases. That of x/2Li₂CO₃+BaTiO₃ decreases by the small addition of Li, but increases by the large addition of Li. All Li⁺‐doped ceramics show antiferroelectric‐like double hysteresis loops. The shape of loops and the dielectric properties are also dependent on the Li site. We suggest that the role of oxygen vacancy accompanied by the Li‐doping is important. By comparison with the results of 3 type ceramics, it is concluded that at x/2Li₂CO₃+BaTiO₃ ceramics, the Li⁺ prefers to favorably substitute Ba²⁺ at A site for the low concentration of Li but its location was changed to Ti⁴⁺ site for the high concentration of Li.     

Preparation and Application of Strong Near‐Infrared Emission Phosphor Sr3SiO5:Ce3+,Al3+,Nd3+

This work investigated the near‐infrared (NIR) emission properties of mCe³⁺, xNd³⁺ codoped Sr_3?m?x(Si_1?m?xAl_m+x)O₅ phosphors. Samples with various doping concentrations were synthesized by the high‐temperature solid‐state reaction. Al³⁺ ions have the ability to promote Ce³⁺ ions to enter into the Sr²⁺ sites and to improve the visible emission of Ce³⁺. Thus the NIR emission of Nd³⁺ is enhanced by the energy‐transfer process, which occurred from Ce³⁺ to Nd³⁺. The device based on these NIR emission phosphors is fabricated and combined with a commercial c‐Si solar cell for performance testing. Short‐circuit current density of the solar cell is increased by 7.7%. Results of this work suggest that the Sr_2.95Si_0.95Al_0.05O₅:0.025Ce³⁺, 0.025Nd³⁺ phosphors can be used as spectral convertors to improve the efficiency of c‐Si solar cell.     

Influence of doping with various cations on electrical conductivity of apatite-type neodymium silicates

Apatite-type neodymium silicates doped with various cations at the Si site, Nd₁₀Si₅BO_27?δ (B=Mg, Al, Fe, Si), were synthesized via the high-temperature solid state reaction process. X-ray diffraction and complex impedance analysis were used to investigate the microstructure and electrical properties of Nd₁₀Si₅BO_27?δ ceramics. All Nd₁₀Si₅BO_27?δ ceramics consist of a hexagonal apatite structure with a space group P63/m and a small amount of second phase Nd₂SiO₅. Neodymium silicates doped with Mg²⁺ or Al³⁺ cations at the Si site have an enhanced total conductivity as contrasted with undoped Nd₁₀Si₆O₂₇ ceramic at all temperature levels. However, doping with Fe³⁺ cations at the Si site has a little effect on improving the total conductivity above 873 K. The enhanced oxide-ion conductivity in a hexagonal apatite-type structure depends upon the diffusion of interstitial oxide-ion through oxygen vacancies induced by the Mg²⁺ or Al³⁺ substitution to the Si⁴⁺ site and through the channels between the SiO₄ tetrahedron and Nd³⁺ cations. At 773 K, the highest total conductivity is 4.19×10^?5 S cm^?1 for Nd₁₀Si₅MgO₂₆ ceramic. At 1073 K, Nd₁₀Si₅AlO_26.5 silicate has a total conductivity of 1.55×10^?3 S cm^?1, which is two orders of magnitude higher than that of undoped Nd₁₀Si₆O₂₇.     

Phase transformation and grain-boundary segregation in Al-Doped Li7La3Zr2O12 ceramics

Cubic phase garnet-type Li₇La₃Zr₂O₁₂ (LLZO) is a promising solid electrolyte for highly safe Li-ion batteries. Al-doped LLZO (Al-LLZO) has been widely studied due to the low cost of Al₂O₃. The reported ionic conductivities were variable due to the complicated Al³⁺-Li⁺ substitution and Li_xAlO_y segregation in Al-LLZO ceramics. This work prepared Li_7?3xAl_xLa₃Zr₂O₁₂ (x = 0.00~0.40) ceramics via a conventional solid-state reaction method. The AC impedance and corresponding distribution of relaxation times (DRT) were analyzed combined with phase transformation, cross-sectional microstructure evolution, and grain boundary element mapping results for these Al-LLZO ceramics to understand the various ionic transportation levels in LLZO with different Al-doping amounts. The low conductivity in low Al-doped (0.12~0.28) LLZO originates from the slow Li⁺ ion migration (1.4~0.25 μs) in the cubic-tetragonal mixed phase. On the other hand, LiAlO₂ and LaAlO₃ segregation occur at the grain boundaries of high Al-doped (0.40) LLZO, resulting in a gradual Li⁺ ion jump (6.5 μs) over grain boundaries and low ionic conductivity. The Li_6.04Al_0.32La₃Zr₂O₁₂ ceramic delivers the optimum Li⁺ ion conductivity of 1.7 × 10^?4 S cm^?1 at 25 °C.     

Structure and microwave dielectric properties of BaAl2−2xLi2xSi2O8-2x ceramics

BaAl_2-2xLi_2xSi₂O_8-2x (x = 0, 0.005, 0.0075, 0.01, 0.02, 0.03) ceramics were synthesized by solid-state sintering method. Based on density functional theory, the first-principle calculations provided by the Cambridge Sequential Total Energy Package (CASTEP) software were introduced to the BaAl₂Si₂O₈ (BAS) system. In an effort to confirm the site occupied by Li⁺, we discussed the formation energy and final energy of different positions of Li⁺ doped BAS. The result demonstrated that Li⁺ should substitute Al³⁺ to promote the hexacelsian-to-celsian transformation with the aid of generated oxygen vacancies. The sintering behavior, crystal structure, surface appearance, and microwave dielectric properties of samples were investigated. Completely transformed celsian could be obtained when x = 0.005–0.03, which lowered the sintering temperature from 1400 °C (x = 0) to 1300 °C (x = 0.03), as well as strikingly improved the compactness, quality factor (Q × f) value and temperature coefficient of resonant frequency (τ_f) of BAS ceramics. When x = 0.1, unveiling the significant effects of Al-position ion substitution, BaAl_1.98Li_0.02Si₂O_7.98 ceramic sintered at 1350 °C for 5 h exhibited a supreme Q × f value of 48,620 GHz, and the ε_r and τ_f values were 6.99 and -23.29 × 10^?6 °C^?1, respectively.     

Effect of Sintering Additives on Relative Density and Li‐ion Conductivity of Nb‐Doped Li7La3ZrO12 Solid Electrolyte

Lithium ion conductors with garnet‐type structure are promising candidates for applications in all solid‐state lithium ion batteries, because these materials present a high chemical stability against Li metal and a rather high Li⁺ conductivity (10^?3–10^?4 S/cm). Producing densified Li‐ion conductors by lowering sintering temperature is an important issue, which can achieve high Li conductivity in garnet oxide by preventing the evaporation of lithium and a good Li‐ion conduction in grain boundary between garnet oxides. In this study, we concentrate on the use of sintering additives to enhance densification and microstructure of Li₇La₃ZrNbO₁₂ at sintering temperature of 900°C. Glasses in the LiO₂‐B₂O₃‐SiO₂‐CaO‐Al₂O₃ (LBSCA) and BaO‐B₂O₃‐SiO₂‐CaO‐Al₂O₃ (BBSCA) system with low softening temperature (<700°C) were used to modify the grain‐boundary resistance during sintering process. Lithium compounds with low melting point (<850°C) such as LiF, Li₂CO₃, and LiOH were also studied to improve the rearrangement of grains during the initial and middle stages of sintering. Among these sintering additives, LBSCA and BBSCA were proved to be better sintering additives at reducing the porosity of the pellets and improving connectivity between the grains. Glass additives produced relative densities of 85–92%, whereas those of lithium compounds were 62–77%. Li₇La₃ZrNbO₁₂ sintered with 4 wt% of LBSCA at 900°C for 10 h achieved a rather high relative density of 85% and total Li‐ion conductivity of 0.8 × 10^?4 S/cm at room temperature (30°C).     

Li ion conduction of perovskite Li0.375Sr0.4375Ti0.25Ta0.75O3 and related compounds

In this work, perovskite-structured Li_0.375Sr_0.4375M_0.25N_0.75O₃ (M=Ti, Sn, N=Nb, Ta) solid electrolytes were synthesized by conventional solid state reaction method. Phase compositions, fractured morphologies and conductivities of these compounds were investigated by X-ray diffraction, scanning electron microscope and AC-impedance spectroscopy, respectively. X-ray diffraction analysis confirms that all of Li_0.375Sr_0.4375M_0.25N_0.75O₃ (M=Ti, Sn, N=Nb, Ta) ceramics present perovskite structure. Pure Li_0.375Sr_0.4375Ti_0.25Ta_0.75O₃ and Li_0.375Sr_0.4375Sn_0.25Ta_0.75O₃ perovskite ceramics were obtained. But impurities were detected in Li_0.375Sr_0.4375Ti_0.25Nb_0.75O₃ and Li_0.375Sr_0.4375Sn_0.25Nb_0.75O₃. Among all investigated compounds, Li_0.375Sr_0.4375Ti_0.25Ta_0.75O₃ shows the highest total ionic conductivity of 2.60 × 10^?4 S cm^?1 at room temperature and the lowest activation energy of 0.347 eV. Conductivities of Li_0.375Sr_0.4375Sn_0.25Ta_0.75O₃ and Li_0.375Sr_0.4375Sn_0.25Nb_0.75O₃ were 4.4 × 10^?5 S cm^?1 and 1.82 × 10^?6 S cm^?1, respectively. Their conductivities were much lower than Li_0.375Sr_0.4375Ti_0.25Ta_0.75O₃ and Li_0.375Sr_0.4375Ti_0.25Nb_0.75O₃.     

Sc- and W-substitution and tuning of phase transition in the Al2Mo3O12

Al₂Mo₃O₁₂ is a typical negative thermal expansion (NTE) material, whose thermal expansion behavior depends on its crystal phase. The thermal shock caused by temperature-induced phase transition limits its wide application. The two series of Al_{2. x}Sc_xMo₃O₁₂ (0 ≤ x ≤ 1) and Al₂Mo_3-xW_xO₁₂ (0 ≤ x ≤ 2.5) solid solutions with controllable phase transition temperature were synthesized via single cation substitution at the A or B position. The problem of thermal shock caused by the change of temperature is effectively solved in the synthesized Al_1.6Sc_0.4Mo₃O₁₂ and Al₂Mo_0.5W_2.5O₁₂, showing stable NTE performance above room temperature, and the coefficients of thermal expansion of which are ?2.19 × 10^?6 °C^?1 in 100–550 °C and ?4.25 × 10^?6 °C^?1 in 85–500 °C, respectively. A-site cation substitution is a more effective way to tune the thermal expansion properties of Al₂Mo₃O₁₂, which is attributed to the fact that the bond strength of A-O is weaker than that of B–O in the compound.     

Variation in structures and photoluminescence spectra of BaxEu1−xAl2O4 powders

Barium europium(II) aluminate (Ba_xEu_1?xAl₂O₄) powders were prepared by a solid-state reaction among barium carbonate (BaCO₃), europium oxide (Eu₂O₃), and alumina (Al₂O₃) powders at 1400 °C for 3 h under a mixed gas flow of H₂ and N₂. The powders were characterized by powder X-ray diffraction (XRD), infrared and Raman spectroscopy, and photoluminescence (PL). With increasing Ba²⁺ content in Ba_xEu_1?xAl₂O₄, the structure of Ba_xEu_1?xAl₂O₄ changed from a monoclinic (P2₁) to hexagonal (P6₃) phase. The hexagonal (P6₃22) phase was also observed between the two phases. The XRD pattern of a single Ba_0.6Eu_0.4Al₂O₄ phase, which has not been reported in the literature, was refined by the Rietveld method and its structure was confirmed by selected-area electron diffraction. With increasing x value, the emission peak in the PL spectra of Ba_xEu_1?xAl₂O₄ became weaker (x = 0–0.4) and then more intense (x = 0.6–0.98), and its position showed a blue shift from 520 to 498 nm.     

A lithium aluminium borate composite microwave dielectric ceramic with low permittivity,near-zero shrinkage,and low sintering temperature

A low temperature co-fired dielectric material with low shrinkage during the sintering process can enhance the circuit design of electronic devices. Lithium aluminium borate composite ceramic with a composition of Li₂O:Al₂O₃:B₂O₃ = 1:1:2 (abbreviated: LAB) was prepared by a traditional solid-state reaction method. These ceramics have a low sintering temperature (675–750 °C), low permittivity, and near-zero shrinkage. When the sintering temperature was 725 °C, the LAB ceramics exhibited a small shrinkage of ?2.4% and the best microwave dielectric properties with ε_r = 3.9, Q × f = 35 500 GHz, and τ_?= ?64 ppm/°C. The LAB ceramics sintered at 700 °C have near-zero shrinkage of ? 0.4% and good microwave dielectric properties. The ceramics transformed from (Li₂B₄O₇ and Al₂O₃) to (Li₂Al₂B₄O₁₀ and Li₄Al₄B₆O₁₇) phases with increasing the sintering temperature, which may be the reason why they show marginal shrinkage. In addition, the ceramics could be co-fired with Ag, indicating that this material is a good candidate for low-temperature co-fired ceramic devices.     

Effects of Al2O3 addition on sintering behaviour,microstructure, and physical properties of Al2O3/vitrified bond CBN composite

The effects of Al₂O₃ content on the sintering behaviour, microstructure, and physical properties of Al₂O₃/vitrified bonds (SiO₂–Al₂O₃–B₂O₃–BaO–Na₂O–Li₂O–ZnO–MgO) and Al₂O₃/vitrified bond cubic boron nitride (CBN) composites were systematically investigated using X-ray diffraction, differential scanning calorimetry, dilatometry, scanning electron microscopy, and X-ray photoelectron spectroscopy. Various amounts of Al₂O₃ promoted the formation of BaAl₂Si₂O₈ and γ-LiAlSi₂O₆, increasing the relative crystallinity of the Al₂O₃/vitrified composite from 85.0 to 93.2%, resulting in residual compressive stress on BaAl₂Si₂O₈, thereby influencing the thermal behaviour and mechanical properties of the Al₂O₃/vitrified composite. The bulk density, porosity, flexural strength, hardness, and thermal conductivity of 57.5 wt% Al₂O₃ sintered at 950 °C were 3.12 g/cm³, 6.1%, 169 MPa, 90.5 HRC, and 4.17 W/(m·K), respectively. The coefficient of thermal expansion of the bonding material was 3.83 × 10^?6 °C^?1, which was comparable to that of CBN, and the number of N–Al bonds were increased, which boosted the flexural strength of the Al₂O₃/vitrified CBN composite to 81 MPa. The excellent mechanical properties, compact structure, and suitable interfacial bonding state with the CBN grains of the Al₂O₃/vitrified composite make it a promising high-performance bonding material for superhard abrasive tools.     

Complete Li+ exchange into zeolite X (FAU, Si/Al = 1.09) from undried methanol solution

Complete exchange of Li⁺ into zeolite Na-X, |Na₉₂|[Si₁₀₀Al₉₂O₃₈₄]-FAU, was accomplished using undried methanol solvent (water concentration 0.02 M). A crystal of Na-X was treated with 0.1 M LiNO₃ in the solvent at 333 K, followed by vacuum dehydration at 673 K and 1 × 10^?6 Torr for 2 days. Its structure was determined by single-crystal synchrotron X-ray diffraction techniques, in the cubic space group $ Fd\overline{3} $ at 100(1) K. The 92 Li⁺ ions per unit cell are found at three different crystallographic sites. The 32 Li⁺ ions occupy at site I’ in the sodalite cavity: these Li⁺ ions are recessed 0.28 Å into the sodalite cavity from their 3-oxygens plane [Li–O = 1.903(5) Å and O–Li–O = 117.8(3)°]. Another 32 Li⁺ ions are found at site II in the supercage, being recessed 0.26 Å into the supercage [Li–O = 1.968(5) Å and O–Li–O = 118.3(3)°]. The remaining 28 Li⁺ ions are located at site III in the supercage [Li–O = 2.00(8) Å].     

Improvement of Al3+ ion conductivity by F doping of (Al0.2Zr0.8)4/3.8NbP3O12 solid electrolyte for mixed potential NH3 sensors

New Al³⁺ ion conducting solid electrolytes (Al_0.2Zr_0.8)_4/3.8NbP₃O_12-xF_2x(0?≤x?≤?0.4) with Nasicon-structure are successfully prepared by solid state reaction method. The influences of the doped F^- content on the properties of the (Al_0.2Zr_0.8)_4/3.8NbP₃O_12-xF_2x samples are investigated using X-ray powder diffraction (XRD), scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS). The results show that F^- doping can effectively improve the sinterability and the total conductivity of the (Al_0.2Zr_0.8)_4/3.8NbP₃O_12-xF_2x samples. Among the solids series, (Al_0.2Zr_0.8)_4/3.8NbP₃O_11.7F_0.6 shows the highest conductivity of 1.53?×?10^?3 S?cm^?1at 500?°C, which is approximately 7.9 times higher than that of the undoped (Al_0.2Zr_0.8)_4/3.8NbP₃O₁₂. The ion transference number of the samples is higher than 0.99 at 300–700?°C. On the basis of the promising properties, a mixed-potential type NH₃ sensor based on (Al_0.2Zr_0.8)_4/3.8NbP₃O_11.7F_0.6 electrolyte and In₂O₃ sensing electrode has been developed. The sensing performance of the sensor is evaluated. The mixed-potential type sensor can work at relatively low temperatures of 200–350?°C and an excellent sensitivity of 99.71?mV/decade at 250?°C is obtained. The sensor also displays excellent stability and reproducibility, accompanied by low cross-sensitivities to CO₂, CH₄ and H_2.     

Recent results on lithium ion conductors

Conductivity data for several new lithium ion conductors are presented. Li₃N has a very open structure with intersecting tunnels in 2 dimensions. High ionic conductivity has been found at relatively low temperatures. Data indicate that the conductivity can be improved by suitable doping, as well as stoichiometric control.Solid solutions of Li₄SiO₄ and Li₃PO₄ have also been investigated. The unit cell of Li₄SiO₄ contains two SiO^?4₄ tetrahedra linked by 8 Li ions, which are distributed over 18 possible sites. An improvement of the conductivity of about five orders of magnitude at 100 °C has been obtained at 40 mole % Li₃PO₄.Solid LiAlCl₄ has relatively large values of conductivity in the range from room temperature to its melting point at about 146 °C. Upon melting, the ionic conductivity jumps to over 0.1Ω^?1 cm^?1.Another group of materials are based upon the anti-fluorite structure. Data are presented on Li₂S and Li₂O. The related compounds Li₅AlO₄, Li₅GaO₄, and Li₆ZnO₄ have a partially occupied cation sublattice. The ionic conductivity of these materials rises very rapidly at about 380°C, reaching very high values over 400°C.The large values of ionic conductivity found in some of these materials may lead to their practical use as solid electrolytes.     

Fast synthesis of MgAl2O4‒W and MgAl2O4‒W‒W2B composite powders by self-propagating high-temperature synthesis reactions

MgAl₂O₄?W and MgAl₂O₄?W?W₂B composite powders were obtained rapidly in a single step by self-propagating high-temperature synthesis of WO₃?Mg?xAl₂O₃ and WO₃?B₂O₃?Mg?yAl₂O₃ systems. The addition of various Al₂O₃ contents (x and y-values) to the starting materials was considered as the main synthesis parameter. Thermodynamic calculations revealed that the adiabatic temperature of both systems was decreased with increasing Al₂O₃ content. The XRD results indicated that after acid leaching of the WO₃?Mg?xAl₂O₃ combustion products, W and MgAl₂O₄ were formed as the main phases and WO₂, MgWO₄ and Al₂O₃ as the minor constituents in the final composite. On the other hand, MgAl₂O₄?W composites were synthesized in the WO₃?B₂O₃?Mg?yAl₂O₃ system at y<1.4 mol. By increasing the y-value to 2.1 mol, W₂B was formed as a new product leading to production of MgAl₂O₄?W?W₂B composite. The formation of spinel was confirmed by the Fourier transformed infrared spectroscopy analysis. Microstructure observations represented the uniform distribution of MgAl₂O₄ blocks within the fine spherical W particles. The melting of Al₂O₃ was found as a vital step for rapid synthesis of MgAl₂O₃ by the SHS route. Finally, the possible formation mechanism of MgAl₂O₄ during the combustion synthesis was proposed.     

Structural and electrochemical characteristics of Li4−xAlxTi5O12 as anode material for lithium-ion batteries

Al-doped Li₄Ti₅O₁₂ in the form of Li_4−xAl_xTi₅O₁₂ (x = 0, 0.05, 0.1 and 0.2) was synthesized via solid state reaction in an Ar-flowing atmosphere. Al-doping does not change the phase composition and particle morphology, but easily results in the lattice distortion and thus the poor crystallinity of Li₄Ti₅O₁₂. Al-doping decreases the specific capacity of Li₄Ti₅O₁₂, while improves remarkably its cycling stability at high charge/discharge rate. The substitution of Al for Li site can enhance the electronic conductivity of Li₄Ti₅O₁₂ via the generation of mixing Ti⁴⁺/Ti³⁺, whereas impede the Li-ion diffusion in the lattice. Excessive Al causes large electrode polarization due to the lower Li-ion conductivity, and thus leads to low specific capacity at high current densities. Li_3.9Al_0.1Ti₅O₁₂ exhibits a relatively high specific capacity and an excellent cycling stability.     

Relationship between glass network structure and conductivity of Li2O-B2O3-P2O5 solid electrolyte

Solid state glass electrolyte, xLi₂O-(1 − x)(yB₂O₃-(1 − y)P₂O₅) glasses were prepared with wide range of composition, i.e. x = 0.35 - 0.5 and y = 0.17 - 0.67. This material system is one of the parent compositions for chemically and electrochemically stable solid-state electrolyte applicable to thin film battery. Lithium ion conductivity of Li₂O-B₂O₃-P₂O₅ glasses was studied in the correlation to the structural variation of glass network by using FTIR and Raman spectroscopy. The measured ionic conductivity of the electrolyte at room temperature increased with x and y. The maximum conductivity of this glass system was 1.6 × 10⁻⁷ Ω⁻¹ cm⁻¹ for 0.45Li₂O-0.275B₂O₃-0.275P₂O₅ at room temperature. It was shown that the addition of P₂O₅ reduces the tendency of devitrification and increases the maximum amount of Li₂O added into glass former without devitrification. As Li₂O and B₂O₃ contents increased, the conductivity of glass electrolyte increased due to the increase of three-coordinated [BO₃] with a non-bridging oxygen (NBO).