Ternary Tin Research Articles

Unraveling the atomic-level manipulation mechanism of tin-based ternary anodes via hetero-anion engineering for stable sodium ion storage

The gradual retardation of heterogeneous interface reactions during extended cycling results in significant capacity loss, particularly in the initial few cycles. This is due to the inhomogeneous distribution and structural degradation of heterointerfaces. Currently, a range of atomic-level tuning strategies are employed to enhance the intrinsic transfer characteristics for sodium-ion batteries (SIBs). Herein, the defect-rich single-phase ternary tin sulfide selenide (SnSe1.33S0.67) anode is constructed via favorable heteroatom(S) introducing. Such a defective open structure employed as anodes for SIBs, delivers a superior rate performance of 452.3 mAh g−1 at 5.0 A g−1, and excellent cycling stability, with a capacity retention of 535.8 mAh g−1 after 500 cycles at 1.0 A g−1. The exceptional performance is attributed to the rapid diffusion of ions/electrons through lattice defects and heteroatom coexistence, as well as the high tolerance for volume changes resulting from optimized phase transition modes and enhanced structural rigidity, as demonstrated by experimental results and density functional theory (DFT) calculations. Through the heteroatoms injection strategy, this work offers deeper insights into the correlation between precise regulation of internal defects and superior storage performance in SIBs.

A prediction of Young's modulus for tin containing phosphate glasses using quantitative structural information

A rigid unit packing fraction (RUPF) model was used to better understand the influence of local structural units on the Young's elastic modulus (E) of binary and ternary tin phosphate glasses. Quantitative analyses of the units that constitute the glass structure, obtained from X-ray/neutron diffraction and 31P MAS-NMR spectroscopy, were used to calculate polyhedral packing fractions that, with tabulated bond dissociation energies, were used to predict E based on a modification of the Makashima-Mackenzie relationship, which uses ion sizes to calculate packing fractions. Predictions based on the RUPF model are better than those based on ion sizes, and extending the RUPF model to all cation-polyhedra accounts for the compositional dependence of the Sn-coordination number.

Solution-Processed Ternary Tin (II) Alloy as Hole-Transport Layer of Sn-Pb Perovskite Solar Cells for Enhanced Efficiency and Stability.

Tin-lead (Sn-Pb) narrow-bandgap (NBG) perovskites show great potential in both single-junction and all-perovskite tandem solar cells. Sn-Pb perovskite solar cells (PSCs) are still limited by low charge collection efficiency and poor stability. Here, a ternary Sn (II) alloy of SnOCl is reported as the hole-transport material (HTM) with a work function of 4.95eV for Sn-Pb PSCs. The solution-processed SnOCl layer has a texture structure that not only reduces the optical loss of the devices, but also changes grain growth of Sn-Pb perovskites and boosts the carrier diffusion length to 3.63µm. The formation of small perovskite grains at the HTM/perovskite interface is suppressed. These result in an almost constant internal quantum efficiency (IQE) of 96 ± 2% across the absorption spectrum of Sn-Pb perovskites. The SnOCl HTM significantly enhances the stability of Sn-Pb PSCs with 87% of its initial efficiency retained after 1-sun illumination for 1200h, and keeps 85% efficiency under 85°C thermal stress for 1500h. The hybrid HTM further improves the stabilized efficiencies of single-junction Sn-Pb PSCs and all-perovskite tandem solar cells to 23.2% and 25.9%, respectively. This discovery opens an avenue to the multicomponent metal alloys as HTM in PSCs.

Luminescence and structural evolution in ultra‐low melting quaternary tin fluorophosphate glasses (NaF‐SnF2‐SnO‐P2O5)

AbstractFor transparent low melting inorganic glass, which is relevant for sealing and additional applications, Pb‐containing glasses have reached the lowest melting point and best comprehensive performance. Considering potential toxicity and regulatory limitations, there is urgent need to develop Pb‐free ultra‐low melting point glass. Herein, we systemically investigated the structure and luminescence evolution of the Pb‐free ultra‐low melting quaternary tin fluorophosphate glasses (NaF‐SnF2‐SnO‐P2O5), in which varied NaF content was tuned to affect the properties of glass. With NaF content increases, the Sn‐O and P‐O bonds have been gradually transformed to Sn‐F and P‐F bonds, and the phosphrous tetrahedron PO4 has been converted to PO3F. The weaken bonding results in the decrease of the ultra‐low melting point to 329°C when NaF increased to 15 a.t.%, 29oC lower than the ternary glass. The blue shifts of both absorption and photoluminescence spectra were observed due to the higher ionic character of glass structure with NaF increases. As reported previously in the ternary tin fluorophosphate glass, the quaternary glass system also shows a phosphorescence behavior (∼1 s) due to the existence of oxygen vacancies. Additionally, the changes in oxygen vacancy defects correlate with the NaF content, thus affecting the decay time as well. The ultra‐low melting point luminescent quaternary tin fluorophosphate glasses (NaF‐SnF2‐SnO‐P2O5) may be relevant for opto‐electronic applications such as the packaging in displays or light‐emitting diodes.

Tunable and high-performance self-powered ultraviolet detectors using leaf-like nanostructural arrays in ternary tin zinc sulfide system

Recently, self-powered ultraviolet (UV) detectors have received increasing attention for developing the future demands for optoelectronic devices due to their distinguished photoresponse properties. In this study, an emerging type of self-powered UV detectors using the ternary SnxZn1-xS alloy thin films (0.20 ≤ x ≤ 0.40 mol) were fabricated using the solvothermal process. The structural study showed the formation of two distinct phases of ZnS and SnS for the samples with high content Sn2+ ions. According to the ideal crystal-growth mechanism proposed by periodic bond chain theory, a morphological evolution from nanorods to nanoflakes and unique aligned three-dimensional leaf-like nanostructures was achieved by enhancing the Sn2+ content up to the maximum value of 0.40 mol. The optical properties featured the less influence of band tailing on the band gap energy at the high concentration of Sn2+ ions, resulting in the widening of the band gap energy up to 4.56 eV thanks to the Burstein-Moss effect. From the photosensing measurements, the Schottky barrier heights of the devices were found to significantly reduce under UVB exposure as the Sn2+ content increases, confirming a high Ion/Ioff ratio (>103) for the devices. The UV detectors exhibited superior self-powered characteristics under UVB illumination, having high photosensitivity and fast photoswitching response times (τr = 1.9 and τd = 2.6 ms) at zero voltage. Interestingly, the photoresponse performance of UV detectors can be adjusted by varying the content of Sn2+ ions, which signifies that tunable self-powered UV detectors can be designed by varying the Sn2+ concentration in the ternary SnxZn1-xS system.

Sn3B8O15: A Ternary Tin(II) Borate with Flexible [B8O18]12- Fundamental Building Block Formed by [B7O16]11- and [BO3]3- Groups.

Owing to the tendency to form the glass state in growing crystals in the ternary tin(II) borate system, hitherto, very few single crystals in ternary tin(II) borate were reported. In this paper, a single crystal of Sn3B8O15 was obtained via a high temperature solution method in a closed system. The structure features a flexible fundamental building block [B8O18]12- constructed by one [BO3]3- unit and one [B7O16]11- group that contains three hexatomic rings, which further connect to compose a two-dimensional 2∞[B8O15] layer structure. The connection mode and flexibility of the three hexatomic B-O rings were analyzed, verifying the structural diversity of the B-O configuration. Moreover, the synthesis, crystal structure, and various characterizations were comprehensively presented. Also, theoretical calculations were employed to discuss structure-property relationships, and we use the real-space atom-cutting techniques to explain the origin of the birefringence of Sn3B8O15.

One-pot synthesis of tin chalcogenide-reduced graphene oxide-carbon nanotube nanocomposite as anode material for lithium-ion batteries.

In this study, a ternary tin chalcogenide (TC)-reduced graphene oxide (RGO)-carbon nanotube (CNT) nanocomposite was synthesized as a lithium-ion battery (LIB) anode by a simple one-step protocol. The nanocomposite was prepared through a hydrothermal method using tin chloride as the tin precursor, thiourea as the sulfur source and reducing agent, and GO-CNT hybrid as the carbonaceous nanostructure. The structure, morphology, and phase analysis of the synthesized nanocomposite powder were investigated using Raman spectroscopy, field-emission scanning electron microscopy (FESEM), and X-ray diffraction (XRD). The results show that GO is reduced while SnS and SnS2 nanosheets along with SnO2 nanoparticles are simultaneously formed within the RGO-CNT hybrid framework throughout the hydrothermal process. During the first lithiation-delithiation process, the discharge capacity and the columbic efficiency for the ternary TC-RGO-CNT nanocomposite electrode at a current density of 50 mA g-1 are 1401 mA h g-1 and 50%, respectively. The TC-RGO-CNT electrode gives an improved capacity of 197 mA h g-1 at 500 mA g-1 while the corresponding value for the bare TC, and binary TC-CNT and TC-RGO nanocomposite electrodes was only 5, 18, and 41 mA h g-1, respectively. Meanwhile, the ternary nanocomposite anode indicates outstanding stability after 150 cycles with a reversible capacity of 100 mA h g-1 at 500 mA g-1. The excellent electrochemical performance of the ternary TC-RGO-CNT nanocomposite is ascribed to the synergistic effect of the high capacity of electrochemically-active TC nanostructures along with the large surface area, porous structure, and exceptional conductivity of the 3D RGO-CNT framework.

The very first normal-pressure tin borate Sn3B4O9, and the intermediate Sn2[B7O12]F.

Aside from amorphous phases, only a single crystalline tin borate had been synthesised so far under high pressure. In this work, we present the very first crystalline ternary tin borate Sn3B4O9 synthesised under ambient pressure by decomposition of Sn3[B3O7]F above 500 °C. The crystal structure of Sn3B4O9 (P21/c, Z = 4, a = 768.07(3) pm, b = 1206.78(4) pm, c = 924.96(3) pm, β = 101.847(1)°, 10 550 data, 147 parameters, R1 = 0.028) determined by single-crystal X-ray diffraction comprises open layered borate polyanions with Sn(ii) ions in-between showing the presence of a stereochemically active lone pair. Sn3B4O9 was further characterized by DFT calculations and vibrational spectroscopy. Its optical band gap was calculated to approx. 3.5(1) eV. Tin borate was gained by thermal decomposition of Sn[B2O3F2] via a further new tin borate fluoride Sn2[B7O12]F (C2/c, Z = 8, a = 1037.99(2) pm, b = 859.78(2) pm, c = 2370.71(8) pm, β = 93.5650(10)°, 2674 data, 199 parameters, R1 = 0.045).

Asymmetric-Layered Tin Thiophosphate: An Emerging 2D Ternary Anode for High-Performance Sodium Ion Full Cell.

The emerging sodium ion batteries (SIBs) are believed to be prospective substitutes for lithium ion batteries (LIBs) because of the wide distribution of sodium resources. However, to compensate for the sluggish reaction kinetics and higher intrinsic potential of Na+ compared to Li+, cost-effective, reliable, and sustainable electrode materials must be explored for practical applications. Herein, 2D ternary tin thiophosphate (SnP2S6) nanosheets (∼10 nm thickness) grown on graphene (denoted as SPS/G hybrid) are demonstrated as intriguing anodes for SIBs. The asymmetric-layered structure and ternary composition enable the SPS/G hybrid with a high reversible capacity (1230 mAh g-1 at 50 mA g-1), superior rate capability (200 mAh g-1 at 15 A g-1), and an exceptional capacity retention of 76% after 1000 cycles at 2.0 A g-1. More importantly, a prototype sodium-ion full cell constructed by pairing with the Na3V2O2(PO4)3F cathode affords a high capacity of 470 mAh g-1 at 30 mA g-1 (on the basis of anode weight) and good cyclic capacity of 360 mAh g-1 at 150 mA g-1. Such 2D ternary chalcogenides with low-cost elements are promising materials for superior SIBs.

Amorphous Films of Ternary Zinc and Tin Oxides for Transparent Electronics

Amorphous films of two varieties of zinc stannate (ZnSnO3 and Zn2SnO4) have been considered that were fabricated by radio-frequency sputtering of ceramic compound targets containing ZnO and SnO2 in 1: 1 and 2: 1 ratios. The elemental and phase compositions of the films and their optical and electrical parameters were determined. The transparency of the films in the visible spectral range is on average 87%. Zinc stannate amorphous films have a high electrical conductivity in contrast to amorphous ZnO and SnO2. This phenomenon, which makes it possible to use zinc stannate amorphous films in transparent and flexible electronics, is explained.

Ternary tin selenium sulfide (SnSe0.5S0.5) nano alloy as the high-performance anode for lithium-ion and sodium-ion batteries

Metal sulfides have received tremendous attention due to their superior electrochemical performance. In this study, it is the first time that the ternary tin selenium sulfide, SnSe0.5S0.5, is investigated as a potential high-performance anode material for lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs). The SnSe0.5S0.5/C nanocomposites have also been synthesized through a facile polyol-method followed by a simple hydrothermal process and subsequent sintering. The material demonstrated a high specific capacity and a long-term cycling stability in both Li-ion and Na-ion batteries (625mAhg−1 for LIB at 500mAg−1 rate after 1000 cycles, 430mAhg−1 in a SIB at 200mAg−1 rate after 100 cycles). Furthermore, the kinetic analysis of Li-ions and Na-ions storage revealed that the extrinsic pseudocapacitive contribution could improve the charge transfer rate during the insertion and extraction of Li-ion and Na-ion, thus enhancing the rate performance and cycling stability. These results demonstrated that the novel tin selenium sulfide (SnSe0.5S0.5) material could potentially be an excellent anode material for Li-ion storage and Na-ion storage.

Investigation on lithium conversion behavior and degradation mechanisms in Tin based ternary component alloy anodes for lithium ion batteries

In this article, we investigate into the ternary tin based alloy, thin film anodes for lithium ion batteries, specifically into Sn-Sb-Cu system, synthesized via electrodeposition. The alloy electrodes show a stable discharge capacity of ∼600 mAh g−1 discharged at a rate of 200 mA g−1 (∼0.3C) for 50 cycles. FESEM images show a nano-dendritic, porous microstructure which can help in accommodating high volume expansion during lithiation and prevent the problem of pulverization. The phases present in the prepared anodes are Sn, SnSb and Cu6 Sn5 which are all active towards lithium insertion and extraction. The behavior of this multi-phase alloy system is examined using X-ray diffraction measurements. At extremely slow discharge rates, the phases take up lithium at distinct potentials with reactions with SnSb, Cu6Sn5 and Sn occurring at 0.86 V, 0.65 V and 0.45 V, respectively. A mechanism, where a lithiated phase decomposes and internally supplies lithium to the reacting phase, is observed and thereby lowering the total specific capacity of the anode as a whole when discharged. EIS measurements further reveal that there is degradation in the reaction kinetics with increasing cycles. Finally, failure of the anode is investigated and the cause is identified as the delamination of active material from the current collector. The problem is successfully removed by replacing Copper current collector with Silver current collector, where the intermetallic composition reacts at a lower voltage than Tin. Cycling the anode above this cutoff voltage removes the problem of delamination. However, it is identified that the existing electrolyte composition in the market, used for graphite anodes, is incompatible with Tin based anodes.

Disappearance of Localized Valence Band Maximum of Ternary Tin Oxide with Pyrochlore Structure, Sn2Nb2O7

The electronic structure of ternary tin oxide with pyrochlore structure, Sn2Nb2O7, which has the contribution of the Sn 5s orbitals in the valence band, is examined by synchrotron-radiation-excited photoelectron spectroscopy and X-ray absorption spectroscopy together with ab initio calculations. The empirical spectra are qualitatively consistent with the calculated density of states with the exception of a striking discrepancy in the electronic structure around the valence band maximum (VBM). The band calculation suggests the presence of a sharp peak around the VBM, mainly due to dispersionless bands that are derived from hybridization of Sn 5s orbitals and O 2p orbitals close to the Sn atom. However, the photoelectron spectra show no such characteristic spectral feature. From the theoretical prediction about the orbital origin of the localized VBM and the experimental estimation of the elemental composition by chemical analysis, it seems reasonable to conclude that the discrepancy of the electronic struc...

Structural, Electronic, and Optical Properties of K2Sn3O7 with an Offset Hollandite Structure.

We present the compound K2Sn3O7, a Sn4+-containing oxide with a unique structure type among oxides. The compound is orthorhombic and reminiscent of an offset hollandite, where open channels hold a row of four K+ per channel per cell. UV-visible spectroscopy indicates a wide band gap semiconductor, which is confirmed by first-principles electronic-structure calculations of band structures, densities of states, and optical properties. The continued discovery of new structure types in ternary tin oxides should remain a priority for the identification of prospective ion conductors and transparent conducting compounds.

New investigation on the physical and electrochemical properties of (TAS) thin films grown by electrodeposition technique

Abstract The purpose of this work was to develop a new method on the synthesis of ternary tin antimony sulfide (TAS) thin films on indium tin oxide (ITO) coated glass substrates using one-step electrodeposition route. To explore the mechanism behind, a cyclic voltammetric study was performed in unitary (Sn, Sb, S) systems, binaries (Sn-S, Sb-S) systems, and ternary Sn-Sb-S system. The effect of various deposition potentials (E dep ) on the structural, optical and morphological properties, as well as frequency response has been investigated by X-ray diffraction patterns, UV–vis spectroscopy, scanning electron microscope (SEM), and electrochemical impedance spectroscopy (EIS). From these results, X-ray diffraction demonstrates that the major crystalline phase of the SnSb 2 S 4 orthorhombic phase has been obtained at E dep = −0.7 V (vs. Ag/AgCl). Based on the (SEM) images, it was found that the surface morphology and grain size were strongly influenced by the deposition potential. According to optical measurements, the (TAS) thin films display good optical properties with direct band gap. An equivalent electric circuit model (EECM) is designed for (EIS) data. The fitting curves are aligned well with the experimental curves, suggesting that the proposed equivalent circuit model is an ideal model for (TAS) electrode.

Microstructural characteristics of tin oxide-based thin films on (0001) Al2O3 substrates: effects of substrate temperature and RF power during co-sputtering.

While tin oxides such as SnO and SnO2 are widely used in various applications, surprisingly, only a limited number of reports have been presented on the microstructural characteristics of tin oxide thin films grown under various growth conditions. In this paper, the effects of the substrate temperature and content of foreign Zn ion on the microstructural characteristics of tin oxide thin films grown by radio-frequency magnetron sputtering were investigated. The increase in substrate temperature induced change in the stoichiometry of the thin films from SnO(1+x) to SnO(2-x). Additionally, the phase contrast in the transmission electron microscopy image revealed that SnO(1+x) and SnO(2-x) phases were alternating in thin films and the width of each phase became narrower at high substrate temperature. The ternary zinc tin oxide thin films were deposited using the co-sputtering method. As the ZnO target power increased, the crystallinity of the thin films became poly-crystalline, and then showed improved crystallinity again with two types of phases.

Highly stable ternary tin–palladium–platinum catalysts supported on hydrogenated TiO2 nanotube arrays for fuel cells

Herein the Pt nanocrystals were synthesized by a high-pressure methanol reduction method onto the hydrogenated TiO2 nanotube arrays pre-treated by Sn/Pd. Then Sn/Pd/Pt ternary catalysts were fabricated by hydrogen treatment. The composite catalysts with a diameter of about 18 nm were located uniformly at the inner nanotubes. The novel catalyst combined with hydrogenated TiO2 nanotube arrays exhibits excellent electro-catalytic activity and high durability. The electrochemical performance of the catalysts after 18,000 potential cycles between 0 and 1.2 V vs. RHE could reach the maximum, and the electrochemical surface area of the catalyst at 18,000 cycles is about 136 m(2) g(-1)Pt+Pd, which is 1.3 folds than the commercial JM Pt/C (104 m(2) g(-1)Pt). Furthermore, there is little decrease in the electrochemical surface area for the catalyst after additional 7300 potential cycles (total 24,300 cycles). In a full cell testing, the fabricated novel electrode with extra-low Pt loading (0.043 mg cm(-2)) generated power as 1.21 kW g(-1)Pt when it is used as the cathode in a fuel cell.

Electrodeposition and electrochemical properties of novel ternary tin–cobalt–phosphorus alloy electrodes for lithium-ion batteries

Porous Sn–Co–P alloy with reticular structure were prepared by electroplating using copper foam as current collector. The structure and electrochemical performance of the electroplated porous Sn–Co–P alloy electrodes were investigated in detail. Experimental results illustrated that the porous Sn–Co–P alloy consists of mainly SnP 0.94 phase with a minor quantity of Sn and Co 3Sn 2. Galvanostatic charge–discharge tests of porous Sn–Co–P alloy electrodes confirmed its excellent performances: at 50th charge–discharge cycle, the discharge specific capacity is 503 mAh g −1 and the columbic efficiency is as high as 99%. It has revealed that the porous and multi-phase composite structure of the alloy can restrain the pulverization of electrode in charge/discharge cycles, and accommodate partly the volume expansion and phase transition, resulting in good cycleability of the electrode.

Anodic properties of tin oxides with pyrochlore structure for lithium ion batteries

Mixed tin oxides, M 2Sn 2O 7 (M = Y, Nd), with cubic pyrochlore structure were synthesized and characterized by X-ray diffraction and SEM. Galvanostatic cycling versus Li metal in the voltage range, 0.005–1.0 V at the current density of 60 mA g −1 showed that the first-discharge capacities are 913 and 722 mA hg −1 whereas the first-charge capacities are 350 and 265 (±3) mA hg −1, for M = Y and Nd, respectively. The corresponding number of moles of recyclable Li are 3.4 and 3.2 for M = Y and Nd. Crystal structure destruction occurs during the first-discharge leading to the formation of nano-particles of Sn-metal and finally Li 4.4Sn in a matrix of Li–M–O. After 50 cycles, both compounds showed a capacity-retention of 89 (±1)% of the 10th cycle reversible capacity. The coulombic efficiency is ∼98%. The average charge and discharge voltages in both compounds are 0.5 and 0.25 V, respectively. Cyclic voltammograms complement the galvanostatic results and showed that a good operating voltage range is 0.005–1.0 V. The electrodic performances of M 2Sn 2O 7 have been compared with those exhibited by other crystalline ternary tin oxides.

Characterisation of electroplated Sn/Ag solder bumps

Environmental concerns as well as legal constraints have been pushing research on flip chip technology towards the development of lead-free solders and also to new deposition techniques [Z.S. Karim, R. Schetty, Lead-free bump interconnections for flip-chip applications, in: IEEE/CPMT 1nternational Electronics Manufacturing Technology Symposium, 2000, pp. 274–278, P. Wölflick, K. Feldmann, Lead-free low-cost flip chip process chain: layout, process, reliability, in: IEEE International Electronics Manufacturing Technology (IEMT) Symposium, 2002, pp. 27–34, M. McCormack, S. Jin, The design and properties of new, pb-free solder alloys, in: IEEE/CPMT International Electronics Manufacturing Technology Symposium, 1994, pp. 7–14, T. Laine-Ylijoki, H. Steen, A. Forsten, Development and validation of a lead-free alloy for solder paste applications. IEEE Transactions on Components, Packaging, and Manufacturing technology, 20(3) (1997) 194–198, D. Frear, J. Jang, J. Lin, C. Zhang, Pb-free solders for flip-chip interconnects, JOM, 53(6) (2001) 28–32].Binary and ternary tin alloys are promising candidates to substitute lead-content components. In this paper, we describe an electroplating technique for high density FlipChip packaging [M. Bigas, E. Cabruja, Electrodeposited Sn/Ag for flip chip connection, CDE (2003)]. An analysis using Auger Electron Spectroscopy (AES) together with additional Energy Dispersive Xray analysis (EDS) tests and Scanning Electron Microscope (SEM) analysis have been performed to optimize the reflow process of the electrodeposited bumps.