Lithium Bismuth Research Articles

Structural investigation of lithium bismuth borate glasses through Raman and infrared spectroscopies

AbstractThe structure of lithium bismuth borate glasses in the compositional series xBi2O3–25Li2O–(75 − x) B2O3 was studied with the use of Raman and infrared (IR) spectroscopies. Transparent glasses formed between x = 0 and 55, whereas glass–ceramics formed between x = 60 and 75 mol% Bi2O3. Structural investigation on the borate network showed that the glasses were undermodified at high Bi2O3 compositions with metaborate, pyroborate, and orthoborate triangles and tetrahedra being present past the stoichiometric orthoborate compositions (O/B = 3). Bi2O3 was found to participate in the glass as both a network former and modifier, as observed in the Raman and IR spectra. Optical absorption spectra of the glasses show a redshift of the absorption edge with increased Bi2O3. Optical, thermal, and physical properties of the glasses were examined and correlated to the structural evolution.

Synthesis and electrical characterization of Sb modified lithium bismuth titanate

Sb-modified lithium bismuth titanate Li0.5Bi0.3Sb0.2TiO3 is prepared following the mixed oxide method. The development of a new compound with a single-phase orthorhombic crystal structure is approved from the XRD analysis at environmental temperature. The electrical behavior like dielectric and electrical conductivity are analyzed in a wide temperature as well as frequency range by the impedance analyzer, which exhibits that these properties effectively depend on frequency and temperature. The ac conductivity versus temperatures plots obeys the Arrhenius relation and confirm the presence of the mixed type of conductivity process like space charge conductivity created from oxygen ion vacancies, ionic-polaronic conductivity, and so on, in the sample. Ac conductivity versus frequency spectra is as per Jonscher’s Universal Power law.

Li–Bi and Li–In alloys-based composite anode for lithium metal batteries

Lithium (Li) metal anode for high-energy-density secondary batteries has gained increasing attention in recent years due to its ultra-high specific capacity and the lowest redox potential. However, the Li anode suffers from severe issues including dimensional instability, Li dendrite growth, and low Coulombic efficiency (CE). In this work, a composite Li electrode (Li–Bi–In) with lithium–bismuth (Li–Bi) and lithium–indium alloys (Li–In) as the lithium host is fabricated to address the dimensional instability of the Li anodes. During Li stripping from the electrode, a porous structure composed of Li3Bi and Li13In3 alloys is formed and sustains the structural integrity. During Li plating, the Li3Bi alloy with high Young's modulus keeps stable, while the Li13In3 alloy with high lithiophilicity and ionic conductivity facilitates Li nucleation and uniform Li plating. Because of the synergistic effect of the two alloys, Li–Bi–In shows remarkable electrochemical performance. The symmetrical cell can stably cycle for more than 1200 h at a high current density of 5 mA cm−2. A full cell with Li–Bi–In anode and Li4Ti5O12 cathode stably runs for 200 cycles. This work provides a facile and effective strategy for fabricating lithium alloy-based composite anodes for lithium metal secondary batteries.

Investigation of physical and optical properties of ZnO doped lithium boro bismuthate glasses

Lithium Bismuth Borate glasses with ZnO addition was examined in relation to their physical, structural, and optical properties from Differential Thermal Analysis and density measurement. Infrared absorption (IR) spectra were recorded to know structural details. The optical properties of these glasses were investigated by UV–VIS absorption spectra. The optical band gap obtained from Tauc’s plots had shown an increasing trend. The rising trend in optical band gap and descendant trend in cut-off wavelength is due to a reduction in NBOs this is evidenced by IR.

Multi-doped ceria-based composite as a promising low-temperature electrolyte with enhanced ionic conductivity for steam electrolysis

A lithium–bismuth–copper co-doped GDC composite (Ce0.712Gd0.178Li0.05Bi0.05Cu0.01O1.801) capable of sintering at ∼750 °C with an electrical conductivity of 29.6 mS cm−1 was developed for the first time for metal-supported solid oxide electrolysers.

Simulation of potential and species distribution in a Li[formula omitted]Bi liquid metal battery using coupled meshes

In this work a 1D finite volume based model using coupled meshes is introduced to capture potential and species distribution throughout the discharge process in a lithium–bismuth liquid metal battery while neglecting hydrodynamic effects, focusing on the electrochemical properties of the cell and the mass transport in electrolyte and cathode. Interface reactions in the electrical double layer are considered through the introduction of a discrete jump of the potential modelled as periodic boundary condition to resolve interfacial discontinuities in the cell potential. A balanced-force like approach is implemented to ensure consistent calculation at the interface level. It is found that mass transport and concentration gradients have a significant effect on the cell overpotentials and thus on cell performance and cell voltage. By quantifying overvoltages in the Li||Bi cell with a mixed cation electrolyte, it is possible to show that diffusion and migration current density could have counteractive effects on the cell voltage. Furthermore, the simulated limiting current density is observed to be much lower than experimentally measured, which can be attributed to convective effects in the electrolyte that need to be addressed in future simulations. The solver is based on the open source library OpenFOAM and thoroughly verified against the equivalent system COMSOL multiphysics and further validated with experimental results.

The dual role of bismuth in Li2O–Bi2O3–B2O3 glasses along the orthoborate join

AbstractThe structures of glasses in the lithium–bismuth orthoborate composition range deviate significantly from the short‐range order structure of the two crystalline end‐members. Although binary Li3BO3 and BiBO3 are solely of comprised trigonal orthoborate anions, all glasses formed by their combination contain four‐coordinated borate tetrahedra. We analyze the structure of (75−1.5x)Li2O–xBi2O3–(25+0.5x)B2O3 glasses in increments of x = 5, with 11B magic‐angle spinning nuclear magnetic resonance (NMR), infrared (IR), and Raman spectroscopy. For the full series, the oxygen‐to‐boron ratio remains constant at O/B = 3:1. NMR quantifies an increase in the fraction of tetrahedral boron with increasing bismuth oxide content. Evolution of the mid‐IR profile suggests multiple types of tetrahedral boron sites. Raman spectroscopy reveals that Bi2O3 tends to cluster within the lithium borate matrix when initially introduced and that this behavior transforms into a bismuthate network with increasing bismuth oxide content. In all cases, mixed Bi–O–B linkages are observed. The dual role of bismuth as network modifier and network former is likewise observed in the far IR. The glass transition temperature continuously increases with bismuth oxide content; however, the glass stability displays a maximum in the multicomponent glass of x = 40.

The Development of Er3+/ Yb3+ Co-Doped Li2O-Bi2O3-Al2O3-B2O3 Glass for Laser and Fiber Optics Applications

The lithium bismuth aluminum borate glasses doped with Er3+ ion (LiBiAlB:Er) were investigated for laser and optical amplifier applications by the Judd–Ofelt and MacCumber theory. The LiBiAlB:Er glass with optimum Er2O3 concentration, 1.0 mol%, then was selected to enhance the luminescence properties by co-doping with the Yb3+ ion. The Er3+/Yb3+ co-doped glasses (LiBiAlB:ErYb) were prepared and studied in the physical, optical, glass network, absorption, and luminescence properties. The glass density tends to increase with addition of Yb2O3 concentration. The FTIR spectra perform the main glass structure which composes of the trigonal BO3 and tetrahedral BO4 borate groups mixing with AlO6 complex. The improvement of absorption coefficient around 977 nm by doping with Yb3+ results in the enhancement of Er3+ emission intensity at 1536 nm wavelength (4I13/2 → 4I15/2). The Yb3+→ Er3+ energy transfer is a significant factor of luminescence development in LiBiAlB:ErYb glass. The MacCumber analysis confirms the high potential for using LiBiAlB:ErYb glass, with Er2O3 1.0 mol% and Yb2O3 2.0 mol%, as an infrared laser medium and a fiber optics amplifier.

Characterization of dielectric relaxation, electrical conductivity and impedance spectroscopy of lead-free Li0.5Bi0.5Ti0.8Zr0.2O3 ceramic

This article focuses on dielectric, electrical, and impedance spectroscopy analysis of lead-free ceramic Zr modified Lithium Bismuth Titanate (Li0.5Bi0.5Ti0.8Zr0.2O3), possessing orthorhombic structure prepared by high-temperature mixed oxide method. The room temperature X-ray diffraction study confirms the formation of a single-phase orthorhombic compound. SEM micrograph shows the homogenous and non-uniform distribution of the grains with grain size 4.9 μm. The dielectric, electrical, and impedance properties of the compound are investigated in a broad frequency (103−106 Hz) and temperature (33 °C–500 °C) range. Dielectric anomaly is observed at 112 °C showing phase transition from ferroelectric to paraelectric state and the maximum value of the dielectric constant is nearly 225 at 10 kHz. Fitted Nyquist plots show the involvement of both bulk and bulk interface to the relaxation processes. The temperature-dependent ac conductivity informs the nature of the variation of conductivity and activation energy in various zones. The impedance loss spectra show the fall in resistance with a rise in temperature which confirms the negative temperature coefficient of resistance (NTCR) nature of the compound. Complex modulus Cole-Cole plots suggest that the presence of a non-Debye type relaxation process which is poly dispersive and in nature.

The Study on Eu3+ Doped Lithium Bismuth Aluminum Borate Glass: New Red Luminescence Medium

The lithium bismuth aluminum borate glasses doped with Eu3+ ion were studied on the physical, structural network, optical and luminescence properties. The glass density fluctuates by following the Eu2O3 content due to the variation of BO4 group in glass network. The FTIR spectra indicate the main glass structure units which occupies by the trigonal BO3 and tetrahedral BO4 borate groups mixing with AlO6 complex. The Eu3+ acts as the glass modifier in glass as the Eu2O3 concentration is higher than 1.00 mol%. The glasses more absorb photons in visible light – near infrared region with addition of Eu2O3 content. Under 394 nm excitation, glasses represented the strongest emission at 613 nm by the 5D0→7F0 transition of Eu3+ and overall color of this emission is red. The optimum concentration of Eu2O3 for this developed glass is 3.00 mol% that owns the highest emission intensity. The Eu3+ doped lithium bismuth aluminum borate glass performs the high potential for using as a red luminescence medium in light sources and display devices.

New lithium bismuth phosphate ceramic: crystal structure, microstructure, microwave dielectric properties and co-firing compatibility with aluminum electrode

New lithium bismuth phosphate ceramic: crystal structure, microstructure, microwave dielectric properties and co-firing compatibility with aluminum electrode

Downshifting analysis of Sm3+/Eu3+ co-doped LiBiAlBSi glasses for red emission element of white LEDs

The Sm3+, Eu3+ single doped, and Sm3+/Eu3+ co-doped lithium bismuth alumino borosilicate (LiBiAlBSi) glasses were prepared by using the melt quenching method and studied photoluminescence (PL) excitation, PL emission, and PL decay to have a better insight into their utility as red emission element for white LEDs. Sm3+ doped LiBiAlBSiSm05 glasses exhibit admirable emission features in the reddish-orange region under n-UV excitation (402 nm). Sm3+/Eu3+ co-doped LiBiAlBSi glasses can be adeptly excited by the blue and n-UV region which is confirmed from the excitation spectrum. In the Sm3+/Eu3+ co-doped LiBiAlBSi glasses, the PL decay lifetime for the Sm3+ emitting level (4G5/2) declines and the energy transfer efficiency increases with an upsurge in Eu3+ ion content, which suggests the energy transfer (ET) process occurs from Sm3+ to Eu3+ ions. The ET process from Sm3+ to Eu3+ ions is also suggested by Dexter's ET method and Reisfeld's approximation by using emission spectra due to non-radiative dipole-dipole (d-d) interaction. The calculated values of CIE chromaticity coordinate for the as-prepared glasses under n-UV excitation shifted from reddish-orange to the red spectral part with the upsurge in Eu3+ concentration. The temperature-dependent PL studies of the optimized LiBiAlBSiSE10 glass revealed its superior thermal stability. All the results obtained finally suggest that, the Sm3+/Eu3+ co-doped LiBiAlBSi glass with 0.5 mol% of Sm3+ ions and 1.0 mol% of Eu3+ ions is a thermally stable candidate to produce intense red color needed to fabricate white LEDs under n-UV and blue excitation through the downshifting process.

Influence of Tb3+ ions concentration and temperature on lithium bismuth alumino borosilicate glasses for green photonic device applications

Lithium bismuth alumino borosilicate (LiBiAlBSi) glasses doped with various concentrations of trivalent terbium (Tb3+) ions were prepared to explore their physical, optical, and photoluminescence (PL) characteristics features. Diffraction pattern recorded for an undoped as well as doped (1.5 mol% of Tb3+) LiBiAlBSi glass ascertained the amorphous nature. Absorption spectra reveal several peaks in n-UV and blue regions. The indirect optical band gap for Tb3+ doped LiBiAlBSi glasses was found in the 3.16-3.46 eV range. PL measurements such as emission (under 378 nm excitation) and excitation (under 542 nm emission) were recorded to study the usage of the as-prepared glasses for green photonic device applications. PL emission spectra reveal four emission bands of Tb3+ ions originating from the excited level of 5D4 to 7FJ (=3,4,5,6) levels. The intensity of the emission peak observed in the green region at 542 nm (5D4→7F5) escalates up to 1.5 mol% of Tb3+ ion concentration and declines beyond due to concentration quenching. Dexter theory applied to the PL emission spectral features reveals dipole-dipole interaction among Tb3+ ions responsible for the transfer of energy and thereby concentration quenching. The CIE coordinates and CCT values calculated for the as-prepared glasses are closure to the values of intense green emission given by the European Broadcasting Union illuminant. The experimental lifetime values (τexp) measured for the intense green emission (5D4→7F5) are reducing with the upsurge in the content of Tb3+ ions in the titled glasses. Correlation of τexp values with the PL emission spectral data facilitate the estimation of radiative properties. Relatively high activation energy value estimated from the temperature-dependent PL show the thermal stability of the optimized glass. The PL (excitation, emission, decay, temperature-dependent) studies along with colorimetric studies confirm the aptness of the LBiAlBSiTb15 glass for photonic applications such as laser and tricolour w-LEDs as a green emitting component.

Gamma ray interaction of optical, chemical, physical behavior of bismuth silicate glasses and their radiation shielding proficiency using Phy-X / PSD program

Three compositions of lithium bismuth silicate glasses containing either 2% PbO, BaO or SrO (all in wt. %) were studied to investigate some of their optical, chemical, and physical properties before and after gamma irradiation. Optical UV transmission, FTIR and ESR spectra have been analyzed and discussed. Also, chemical durability before and after gamma irradiation in acidic, alkaline and neutral solutions has been studied. The results showed relative stability of the glasses on UV-visible, FTIR and ESR spectra. Additionally, good chemical durability in the three leaching solutions was observed especially in the alkaline medium. Many shielding parameters have been investigated such as; mass attenuation coefficient that has been measured experimentally and calculated theoretically using NaI (Tl) detector and Phy-X/PSD software, respectively and the results showed a good agreement of the experimental and theoretical values. Also, some other important shielding parameters have been calculated using the Phy-X/PSD program.

Fabrication, structure, physical and optical features of the 50B2O3 + 25Bi2O3 + (25-x) Li2O + xSrO2 glasses

The purpose of this investigation is to study the physical, structural and optical characteristics of a newly fabricated SrO2 doped lithium bismuth borate glass system. The current glass system was fabricated according to the chemical formula 50B2O3 + 25Bi2O3 + (25-x) Li2O + xSrO2, utilizing the solid state- conventional method. It was noticed that The glass density increased from 4.821 to 5.952 g cm−3 whilst the molar volume was decreasing in the range from 32.93 to 30.44 cm3 mol−1 with increase the SrO2 insertion from 0 (BBLSr0 glasses) to 25 (BBLSr25) respectively. The structure of the fabricated glasses was inspected utilizing X-ray diffraction method which clarified that the insertion of SrO2 didn’t affect the amorphous nature of the tested samples. Furthermore, the UV–vis absorption spectrum was utilized to study the UV absorption characteristics for the fabricated glasses. The UV–vis absorption spectrum showed that the absorption and transition bands increase with insertion of the SrO2 contents. Based on the UV/Vis data, several important optical features were calculated like the energy gap (Eg), Urbach energy (Eu), oscillator energy (Eo) and energy of distribution (Ed). Increasing the SrO2 substitution ratio led to increase the optical properties where the refractive index was found to increase from 3.056 to 5.710.

Acoustoelectronic interaction in metal island films

The interaction of surface acoustic waves with conduction electrons of island films of various metals was investigated. Island films were formed on the surface of piezoelectric crystalline substrates: Lithium Niobate, Bismuth Germanate, and Piezoquartz. It is experimentally obtained that the surface acoustic wave attenuation as a function of film resistance has a characteristic maximum, and that the velocity changes from the velocity at the free surface of the substrate to that at the metallized surface.

Probing of nuclear radiation attenuation and mechanical features for lithium bismuth borate glasses with improving Bi2O3 content for B2O3 + Li2O amounts

Against photon energies extending from 0.015 to 15 MeV, MCNPX, FLUKA and PHITS codes are operated to simulate mass attenuation coefficients (μ/ρ) for a total of ten B2O3-Bi2O3-Li2O glass compositions with added Bi2O3 amount from 10 to 55 mol% (5 mol% growth gradually) as a substitute for total (B2O3 + Li2O) mol% content. All the computed μ/ρ values correctness is examined by Py-MLBUF and WinXCOM programs’ μ/ρ outcomes and we found a good agreement among them. 55Bi2O3-35B2O3-10Li2O (mol%) glass half-value layer (HVL) and mean free path (MFP) quantities are compared with distinct commercial γ-ray attenuating glasses, alloys, polymers, concretes and lead and ceramics corresponding values. Next, equivalent atomic numbers (Zeq) and by employing geometric progression (G–P) fitting method at 1–40 mfp PDs (penetration depths), at 0.015–15 MeV energy range ‘buildup factors’ were calculated. At all chosen twenty-five energies derived radiation protection efficiency (RPE) results assured investigated samples exemplary competence for low energy photons absorption. Applying SRIM codes ΨP and ΦP and ΨA and ΦA (mass stopping powers (MSPs) and projected ranges (PRs) for protons and α-particles), and making use of ESTAR database ΨE (electron MSP) and continuous slowing‐down approximation (CSDA) range for electrons are determined at KE (kinetic energy) range of 0.015–15 MeV. Moreover, fast neutron removal cross-sections (ΣR), for 0.0253 eV energy neutrons absorption cross-sections have been estimated. Deduced ΣR was altered at 0.1105–0.1205 cm−1 range with Bi2O3 inclusion in studied samples. 10Bi2O3-70B2O3-20Li2O (mol%) glass has greater total cross-section (=23.251 cm−1) for thermal neutrons absorption while 55Bi2O3-35B2O3-10Li2O (mol%) sample exhibits quality shielding factors for photons and fast neutrons confirming the included Bi2O3 positive impact. Along with nuclear attenuation features various physical and mechanical aspects are also inspected. Derived Vm (molar volume), OPD (oxygen packing density), Vo (oxygen molar volume), Vt (packing density) and Gt (dissociation energy per unit volume) values indicated glasses rigidity. Following Makishima–Mackenzie's theoretical model primary mechanical features like Y, K, S and L (Young's, bulk, shear and longitudinal modulus) and σ (Poisson's ratio) are evaluated where 10Bi2O3-70B2O3-20Li2O (mol%) glass shows better elastic moduli in all samples.

Influence of Bi2O3/WO3 substitution on the optical, mechanical, chemical durability and gamma ray shielding properties of lithium-borate glasses

Six different lithium bismuth boro-tungstate glasses with chemical composition 20Li2O-(20-x)Bi2O3-xWO3-60B2O3 (x = 0, 1, 2, 3, 4 and 5 mol%) were produced by the quenching method. Then, the glasses were investigated by means of their optical, mechanical, chemical durability and gamma ray shielding properties. Measured values of density and ultrasonic velocities were used to determine the elastic properties of the glasses. The optical band gap determined using the absorbance spectrum fitting (ASF) model was found to decrease under Bi2O3/WO3 substitution. The presence of BO3, BO4, BiO6, and WO4 structural groups in the glasses was confirmed by Fourier transform infrared spectroscopy (FTIR). The dissolution rate in the glass 20Li2O–15Bi2O3–5WO3–60B2O3 (LBWB5) was found to be 10 times lower than 20Li2O-20Bi2O3– 60B2O3. Mass attenuation coefficients (MAC) values of the produced glasses were determined using the MCNPX Monte Carlo code and Phy-X/PSD program. The photon attenuation parameters such as half value layer (HVL), mean free path (MFP), effective atomic number (Zeff), exposure buildup factor (EBF) and energy absorption buildup factor (EABF) were also studied. The obtained results showed that Bi2O3/WO3 substitution has a direct impact on the photon attenuation abilities of produced glasses. More specifically, HVL values increased from 0.252 × 10−2 cm for LBWB0 glass to 0.275 × 10−2 cm for LBWB5 glass. However, different trends were observed for the photon buildup factors for the produced glasses. It can be concluded that the produced glasses have promising structural, optical, and photon attenuation properties to be used for gamma shielding applications.

Concentration-dependent reddish-orange photoluminescence studies of Sm3+ ions in borosilicate glasses

Abstract This paper elucidates the concentration-dependent photoluminescence properties of samarium ions in Lithium bismuth alumino borosilicate (LiBiAlBSi) glasses using XRD, FT-IR, absorption, excitation, emission & decay to quantify the luminescence properties of the titled glasses. XRD and FT-IR spectral data ascertain the non-crystalline nature and vibrational energies in host glass respectively. The intense excitation band observed at 400 nm in near UV region (under λem = 600 nm) is employed to read the emission spectra. Under 400 nm intense excitation wavelength, the titled glasses show intense visible reddish-orange emission at 600 nm. From the emission spectra, it is observed that 0.5 mol% of Sm3+ ions concentration in LiBiAlBSi glass is optimum for reddish-orange emission. The CIE coordinates estimated for LiBiAlBSi glasses are in good proximity with the reddish-orange emission coordinates specified by Nichia Corporation. Branching ratios, emission cross-sections, quantum efficiency, and CIE coordinates estimated finally reveals the aptness of the LiBiAlBSi glasses for reddish-orange optoelectronic device applications.

Structural and Mechanical Properties of Lithium Bismuth Borate Glasses Containing Molybdenum (LBBM) Together with their Glass–Ceramics

This study reports that MoO3 doped glasses (LBB) are produced by a melting traditional process and using the XRD diffractometer technique to check their states. FTIR spectral analysis has examined the functional groups of the glass matrix. FT-IR spectrums reveal that the BO3, BO4. BiO6 and MoO6 octahedral have been built up and structural unit BO3 was transformed into BO4. The mechanical characteristics were linked to the FT-IR spectrum results. Ultrasonic velocities, elastic modulus, density, and thermal stability increased, while molar volume decreased. The increase in these parameters is linked with [BO4] the formation of structural units, an increase the strength of Mo – O, and force constant is higher than Li – O, so glass rigidity increases. Therefore, the increase of MoO3 usually has a significant influence on the bridging oxygen (BO) formation in BBL glasses. The increase in thermal stability connected to an increase in average force constantly, and the replacement of Li–iO with Mo–O linkages. The bond dissociation energy of Li–Li (137.3 ± 6.3 kJ/mol) is much weaker than the dissociation energy of Mo–Mo (449 ± 1 kJ/mol). Lithium borate Li2B4O7 (diomignite) has been identified in all formed glass–ceramics. With the increasing MoO3, the intensity of diomignite diffraction peaks (Li2B4O7) was reduced and transformed into a less stable lithium borate (Li2B2O5) phase.