SnSb Alloy Research Articles

Chloride-Ion-Enriched Solid Electrolyte Interphase with Rapid Na+ Migration toward High-Performance Sodium-Ion Batteries.

Sodium-ion batteries (SIBs) have emerged as potential alternatives to lithium-ion batteries (LIBs), particularly for large-scale applications. Alloy-type anode materials for sodium-ion batteries are esteemed as prospective candidate materials for sodium-ion anodes, owing to their elevated theoretical capacity, heightened utilization efficiency, and minimal production of insulating byproducts. However, the severe volume changes and sluggish ion diffusion kinetics can lead to irreversible particle fragmentation and reaggregation phenomena, ultimately resulting in electrode degradation. Additionally, repetitive volume changes can cause an unstable solid electrolyte interphase (SEI). This study presents the synthesis of chloride-ion-modulated bimetallic SnSb/C nanoparticle anode materials, highlighting the following advantages: (i) Designing a bimetallic SnSb alloy structure serves to buffer the structural stresses generated during sodium insertion/extraction processes, effectively mitigating particle fracture phenomena induced by electrode material expansion/contraction. (ii) Nanostructuring both alloy materials enables the full utilization of active materials and shortens diffusion pathways, thereby significantly enhancing the diffusion rate of sodium ions. (iii) Introducing a carbonaceous matrix serves to alleviate self-agglomeration phenomena of the material during charge/discharge cycles, enhancing the material's conductivity and structural stability. (iv) Utilizing chloride-ion interface modification to achieve a chloride-rich solid-electrolyte interphase (SEI) enhances battery performance.

Clean and sustainable elimination of arsenic–aluminum slag from smelted crude tin via vacuum volatilization – Fractional condensation

In high–tech industries, Sn is an indispensable strategic metal. However, the pyrometallurgical refining process of crude Sn is marred by the production of a substantial amount of hazardous solid waste, primarily As–Al slag, which poses a direct threat to the ecological safety of production areas. To address this problem, this study developed a novel process for that eliminates As–Al slag from a source of crude Sn by employing a vacuum volatilization – fractional condensation process, which was validated by theoretical calculations and laboratory experiments. Theoretically, at system pressures in the 1–10 Pa, the initial volatilization temperatures of Sn, Sb, and As vary significantly. However, the formation of intermetallic compounds can induce the volatilization of Sn. Experimentally, the condensation temperature for Sb was predominantly between 603 K and 810 K, and that for As was between 331.7 K and 484.7 K, which are significantly different ranges. Under optimal experimental conditions, the separation rate of Sb in the Sn–Sb alloy was 93.92%, and the resultant Sn product contained 0.0143% Sb. During the volatilization of the Sn–As alloy, the presence of Sn4As3 compounds impeded the volatilization of As; hoewver, the As content in the Sn product was 0.0053%. In the directional condensation of the As–Sb alloy, the condensation temperatures for As and Sb were similar to those of the pure metals, yielding As and Sb products with purities of 99.99% and 99.95%, respectively. Industrial production trials treating HACT via a continuous vacuum separation – intermittent vacuum separation process achieved direct recovery rates of 72.99% for Sn and 71.15% for Sb, with a total energy consumption as low as 1086 kWh/t. Similarly, the treatment of LACT via a multi–stage continuous vacuum separation process yielded residues that satisfied production standards at a treatment cost of 1187 RMB/t. This entire process requiresno additives, and substantially mitigates the generation of As–Al slag at the source.

Influence of Solidification Parameters and Solute Content on the Machinability of Two Lead-Free Babbit Metals

Studies suggest that white metal Sn-Sb alloys are the most commonly type of babbit metal used in industry. However, it is necessary to evaluate manufacturing characteristics and solute contents that leads the best machining conditions. This work presents a correlation between solidification parameters and machinability of Sn-2.0wt%Sb and Sn-5.5wt%Sb alloys, solidified in a horizontal directional device, evaluating the influence of solute content on these results. Cutting temperatures were measured in dry necking processes along the length of the ingot. It was observed that the reverse cellular-dendritic transition influenced the cutting temperature results. The range of cell and dendrite spacings varies approximately from 40 to 330 μm on the Sn-2.0wt%Sb alloy and from 15 to 240 μm on the Sn-5,5wt%Sb alloy. In the cellular region, higher values are found for the Sn-5.5wt%Sb alloy, but in the dendritic region, these values were higher for the Sn-2.0wt%Sb alloy.

Using Highly Flexible SbSn@NC Nanofibers as Binderless Anodes for Sodium-Ion Batteries

Flexible and binderless electrodes have become a promising candidate for the next generation of flexible power storage devices. However, developing high-performance electrode materials with high energy density and a long cycle life remains a serious challenge for sodium-ion batteries (SIBs). The main issue is the large volume change in electrode materials during the cycling processes, leading to rapid capacity decay for SIBs. In this study, flexible electrodes for a SnSb alloy–carbon nanofiber (SnSb@NC) membrane were successfully synthesized with the aid of hydrothermal, electrospinning and annealing processes. The as-prepared binderless SnSb@NC flexible anodes were investigated for the storage properties of SIBs at 500 °C, 600 °C and 700 °C (SnSb@NC-500, SnSb@NC-600 and SnSb@NC-700), respectively. And the flexible SnSb@NC-700 electrode displayed the preferable SIB performances, achieving 240 mAh/g after 100 cycles at 0.1 A g−1. In degree-dependent I-V curve measurements, the SnSb@NC-700 membrane exhibited almost the same current at different bending degrees of 0°, 45°, 90°, 120° and 175°, indicating the outstanding mechanical properties of the flexible binderless electrodes.

A multi-stage volatilization and condensation process for green and efficient recovery of valuable metals from High-Sb crude Sn

Circulation of Sb in an Sn refining system strongly affects the production process. In this study, an innovative multi-stage vacuum separation process was developed and successfully applied on an industrial scale. Our results indicate that Sn–Sb alloys can be completely separated by vacuum evaporation. In this study, we used single-factor experiments to investigate the effects of distillation temperature and time on several factors, such as the Sn content in the residue, Sb content in the volatile matter, separation rate, and direct recovery rate of Sb from high-Sb crude Sn. The purity of the obtained Sn and Sb products was above 99%, and the recovery rate of the metal was above 99% under the optimal distillation conditions of 1673 K and 150 min. In addition, we suggest that Sn volatilization occurs due to the presence of SbSn intermetallic compounds. A two-stage vacuum-separation process for high-Sb crude Sn was developed for industrial production. Continuous production data showed that the direct yields of Sn and Sb were 72.99% and 71.15%, respectively. The total power consumption of this process was as low as 1086 kWh/t, which is better than the corresponding parameters of other treatment processes.

Interfacial reaction behavior and thermodynamics between Sn-xSb alloys and Cu substrate

In order to determine the effect of Sb element on the welding reliability of Sn-Sb alloy solder, the interfacial behavior of Sn-Sb alloys with different Sb contents on the Cu substrate was investigated. The evolution process of interfacial layers was explained by analyzing the microstructure and interfacial reaction thermodynamics of Sn-xSb/Cu system. The addition of Sb has a non-monotonic effect on the intermetallic compound layers. Sb can inhibit the diffusion of Cu into solder. The addition of 3 wt.% Sb in the alloy reduces the activation energy of interfacial reaction from 286.41 to 62 kJ/mol, which promotes the interfacial reaction. The addition of 10 wt.% Sb increases the activation energy of interfacial reaction to 686.73 kJ/mol, which inhibits the interfacial reaction and reduces the erosion of the Cu substrate by the solder and inhibits the formation of an excessively thick interfacial layer.

Clean and efficient separation process for high-antimony crude tin

Antimony circulates in a tin refining system, which strongly affects the production process. In this study, continuous vacuum separation and discontinuous vacuum separation processes were developed for high-antimony crude tin (HACT). During the industrial treatment of 60 t of HACT, product I of crude Sn and Sn–Sb alloy I were obtained by continuous vacuum separation at a temperature of 1473 K and pressure of 20–100 Pa. Then, Sn–Sb alloy I produced crude Sb and Sn–Sb alloy II via intermittent vacuum separation at 1273 K and 20–150 Pa. Finally, Sn–Sb alloy II was subjected to intermittent vacuum separation without adding any reagents, which generated no waste gas or water. The direct yields of Sn and Sb were 72.99% and 71.15%, respectively, while the total power consumption of the described process was as low as 1086 kWh/t, which were superior to the corresponding parameters of other treatment processes. This paper reports a novel clean and efficient HACT industrial treatment method with an open Sb circuit from the Sn refining system.

In situ three-dimensional cross-linked carbon nanotube-interspersed SnSb@CNF as freestanding anode for long-term cycling sodium-ion batteries

Alloying-based material has achieved tremendous appealing being anode used in sodium‑ion batteries (SIBs) by virtue of its relatively giant sodium storage specific capacity along with low discharge platforms. Nevertheless, the sluggish ion transmission dynamics and the huge volume change during cycling induced irreparable particle pulverization and agglomeration result in collapse of electrode structure and deterioration of cycling properties. In this work, three-dimensional cross-linked carbon nanotube-interspersed SnSb@CNF integrated structure (SnSb@CNF/CNT) is designed and synthesized. In this ingenious nanostructure, CNTs interspersed between CNF frames play the role of electron transport and diffusion “bridges” for enhancing the electrical conductivity of anode materials and relieve aggregation of SnSb alloy particles, the N doped-CNFs serve as external frame could efficiently mitigate dramatic volume effect to maintain system integrity. Based on these constructive advantages, the elastic conductive system can be directly available as anode for SIBs, showing ultralong cycling performance of 210 mAh g−1 over 700 sodiation/desodiation processes with a current density of 0.5 A g−1, even 161 mAh g−1 following 1000 cycling under a high current density of 1 A g−1 accompanied by an almost 100% superb capacity retention ratio, as well as distinguished high rate performance (470 mAh g−1 with a returned current density of 0.05 A g−1). This work shed distinctive insight to construct in situ three-dimensional cross-linked freestanding alloying-based anode materials used in alternative electrochemical grid-scale application.

Towards cost-efficient and scalable fabrication of SbSn/SP@C electrode for sodium-ion batteries

With high capacity and low redox potential, Sn-based materials represent promising anodes for sodium-ion batteries (SIBs). However, the large volume expansion during the cycling process limits their application. Herein, we report a cost-effective, simple, and non-toxic SbSn/SP@C electrode for SIBs via ball milling process and sucrose reduction method. The SbSn/SP@C electrode exhibits high cycle stability and good reversible capacity for SIBs (400.3 mAh g−1 after 100 cycles). Consequently, SbSn/SP@C electrode can afford an effectively carbon-based conductive system, which buffers large volume change of SnSb alloy during the cycling process and provides promising electrochemical performance in Na storage.Graphical abstract

Interfacial Bonding of SnSb Alloys with Graphene toward Ultrafast and Cycle-Stable Na-Ion Battery Anodes

Interfacial Bonding of SnSb Alloys with Graphene toward Ultrafast and Cycle-Stable Na-Ion Battery Anodes

Preparation and properties of SnSb/C/DLC nanofibers with different precursors based on AP-PECVD

In order to explore the morphology and improved electrochemical performance of diamond-like carbon (DLC) deposited on SnSb/C nanofiber derived from different precursors by the atmospheric pressure plasma-enhanced chemical vapor deposition (AP-PECVD) technology. SnCl4•5H2O/SbCl3 (I), Sn(CH3COO)2/Sb(CH3COO)3 (II) were used as SnSb precursors, respectively, the SnSb/C nanofiber membranes were prepared by electrospinning and carbonization, and then DLC was deposited on different SnSb/C nanofibers to obtain SnSb/C/DLC nanofibers. It is shown that the densified and irregular cubic-like DLC nanoparticles were deposited on SnSb/C (I) nanofibers. While on the SnSb/C(II) nanofibers, DLC nanoparticles exhibited as sparse and spherical. Meanwhile, both SnSb/C/DLC nanofibers have good structural stability, especially higher sp3/sp2 ratios DLC was shown in the SnSb/C/DLC (I) nanofiber than that of SnSb/C/DLC (II) one. By comparison, SnSb/C/DLC(I) nanofibers have excellent electrochemical performance, the capacity retention is 69.33% after 100 cycles, and the capacity retention rate from 20 to 100 cycles is 109.24%. This reveals that DLC materials with higher C–C content and uniform distribution have a positive effect on the aspect of inhibiting SnSb alloys volume expansion.

Effect of Cu, Ni, Ag addition on creeping properties of Sn5Sb-0.5Cu-0.1Ni-0.5Ag for high temperature packaging

PurposeThis paper aims to investigate the effect of the Cu, Ni and Ag addition in Sn5Sb-based alloy on the mechanical properties and its mechanism.Design/methodology/approachThe micro-indentation, creeping test of the Cu/Sn5Sb–0.5Cu–0.1Ni–0.5Ag/Cu and Cu/Sn–5Sb/Cu were conducted, and its microstructure was analysed. The scanning electron microscope and the metallographic microscope characterized the microstructure of the Sn5Sb–0.5Cu–0.1Ni–0.5Ag/Cu and Sn–5Sb/Cu joints.FindingsThe microstructure of Cu/Sn5Sb–0.5Cu–0.1Ni–0.5Ag/Cu is distributed with the fine (Cu,Ni)6Sn5 and Ag3Sn intermetallic compounds (IMCs), whereas the Cu6Sn5 and Sn3Sb2 in Cu/Sn–5Sb/Cu is larger and far more less. This investigation reveals that the addition of the Cu, Ni and Ag elements reinforced mechanical properties and provided a technical basis for the development of Sn–Sb alloy with good mechanical properties.Originality/valueThis paper reveals that the hardness and the modulus of the bulk solder Cu/Sn–5Sb/Cu solder joints were improved with the addition of Cu, Ni and Ag trace elements. Meanwhile, the creep resistance and plasticity were also improved. This study has a great value for exploring high-performance Sn–Sb based solder alloy and has proved an example.

Nanoscale localized growth of SnSb for general-purpose high performance alkali (Li, Na, K) ion storage

In this paper, we have successfully encapsulated SnSb alloy nanoparticles into the space of N-doped carbon nanotubes and carbon shells ([email protected]@NC) like a three-dimensional (3D) corn-like structure via a unique method, showing excellent electrochemical storage performance for alkali metal-ion batteries. Here, Sn and Sb can be alloyed with alkali metal ions (Li+/Na+/K+) at different potentials, which can serve as a buffer substrate for each other and inhibit the pulverization of active materials. Pyridine N and pyrrole N in the composite can produce abundant external defects and active sites, which are conducive to accelerating the transmission of alkali metal ions (Li+/Na+/K+). The available space derived from the carbon nanotubes and carbon shells also can effectively alleviate volume change, making high mechanical flexibility and keeping the whole electrode integrity during charge and discharge process. In-situ, ex-situ characterizations and density functional theory (DFT) calculations collectively confirm the excellent reversibility of alkali metal ions storage and fast electrochemical kinetics of the 3D [email protected]@NC composite. Due to the outstanding electrochemical properties, the [email protected]@NC composite can be of great significance for practical design and application in next-generation alkali metal-ion batteries.

First-principles prediction on antimony-doping effects on the cyclic stability of tin anodes for lithium-ion batteries.

Tin-based materials are considered as promising anode materials for advanced Li-ion batteries (LIBs) due to their relatively high capacity and suitable working voltage, but they suffer from poor structural stability during electrochemical cycling. Herein, we present the possibility that the cyclic stability of the Sn LIB anode can be enhanced by adding a small amount of antimony (Sb), based on first-principles investigation of lithiation behavior of amorphous Sn doped with 3 at% Sb. At low Li contents (x < 1.5 in a-LixSn0.97Sb0.03), our simulations show that the preferential reaction of Li with Sb over Sn tends to lead to the formation of small lithiated Sb clusters. However, the aggregated Sb, if any, become fully separated upon further lithiation, implying that they may remain well dispersed in the lithiation/delithiation process if the Sb-doping concentration is sufficiently low. The weak aggregation and preferential lithiation tendency of Sb in the Sb-doped Sn anode can be expected to contribute to enhancing its structural stability during cycling, in comparison with pure Sn and SnSb alloy cases. We also compare lithiation-induced changes in the electrochemical, transport and mechanical properties between the Sb-doped and pure Sn systems. Our study highlights the importance of low concentration and uniform distribution of Sb in order to obtain desired properties of Sb-doped Sn as an anode for LIBs. This finding also provides some hints for the further development of Sn-based anodes via fine-tuning of doping.

Revealing the phase evolution and lithium diffusion in the liquid Sn-Sb electrode

Understanding the phase evolution and mass transfer kinetics at the liquid metal/molten salt interface is of significance for developing liquid metal electrodes, but it is very challenging due to the involving harsh experimental conditions of high temperature and active metals. Herein, an in-situ observation device is set up to monitor the phase evolution of liquid Sn-Sb alloy during its alloying with Li under electrochemical polarization at 550 °C, and a thermodynamic model is used to describe the growth process of solid Li3Sb layer in the Sn-Sb alloy and reveal the correlation of the phase evolution with the discharge equilibrium potential. Using the coulombic titration method, the diffusion coefficient of Li in liquid Sn-Sb alloy is calculated. The diffusion coefficient of Li in liquid Sn-Sb alloy at 550 °C decreases from 13.9 × 10−4 to 1.02 × 10−4 cm2/s when the Li concentration ranges from 0.8 to 20.5 mol.% vs. Sb. Overall, this paper reveals the phase evolution of liquid Sb-Sn electrode during the lithiation process and provides a general method to measure metal diffusion coefficients in liquid metal electrodes.

Composites of SnSb Nanoparticles Embedded in Porous Carbon Nanofibers Wrapped with Reduced Graphene Oxide for Sodium Storage

Alloying-type anode materials are hopeful candidates for sodium (Na)-ion batteries (SIBs) because of their high theoretical capacity by forming Na-rich intermetallic compounds. However, the huge volume changes lead to serious aggregation and crushing of active materials during the cycling process, resulting in a rapid decay in the capacity of the electrode materials. Herein, we report the manufacture of reduced graphene oxide wrapped on the surface of tin–antimony/nitrogen-doped porous carbon nanofibers (SnSb/N-PCNFs/rGO) by a coaxial electrospinning technique and subsequent annealing treatment. The cooperative effect of rGO and PCNFs can greatly relieve the volume expansion of the SnSb alloy in the cycling process and offer more insertion sites for Na+ ions, thus significantly improving the electrochemical performance. As a SIB anode, the SnSb/N-PCNFs/rGO composite exhibits better reversible capacity (maintaining 416 mAh g–1 at 100 mA g–1 after 120 cycles), excellent rate performance, and marvelous cycle performance (up to 303 mAh g–1 at 2000 mA g–1 after 1000 cycles), making it a hopeful anode candidate for SIBs.

Centrifugally spun SnSb nanoparticle/porous carbon fiber composite as high-performance lithium-ion battery anode

A SnSb alloy nanoparticle/porous carbon fiber (PCF) composite was prepared using a novel centrifugal spinning technology with subsequent thermal treatment. In SnSb/PCF composite, the SnSb nanoparticles are uniformly distributed in N-doped carbon fiber matrix due to the created porous structure. The centrifugal spinning can significantly increase the production rate of the fiber composites and the as-prepared SnSb/PCF composite demonstrated small particle size with uniform distribution, mesoporous structure which can facilitate the diffusion of electrolyte and N-doped carbon matrix that is beneficial to the acceleration of the electron transfer. Consequently, SnSb@CFs-20 exhibits a promising electrochemical performance in lithium storage.

Effects of bi-dopants Ni and Fe on tin antimonide alloy anodes: physico and electrochemical studies

The high theoretical capacity of tin antimony (SnSb) alloys in lithium storage has gained a great deal of attention with respect to its application inbattery anodes. , The unstable structure of this alloy in terms of cycling is a huge limitation for this material; however, this can be effectively exterminated by doping with intermetallics. This work reports the improved electrochemical charcteristics of tin antimonide nanoparticles when nickel and iron are incorporated into the matrix. The as-prepared pristine and the Ni and Fe doped SnSb nanoparticles are analyzed in terms of their physiochemical properties via x-ray diffraction (with Rietveld refinement), Raman spectroscopy, Fourier transform infrared spectroscopy, scanning electron microscopy with energy dispersive x-ray analysis. The absence of any metal oxides in the SnSb: Fe, Ni system is confirmed by the x-ray photoelectron spectroscopy. The prepared alloy is subjected as an anode to cyclic voltammetry analysis for both aqueous and non-aqueous electrolytes, and their performance is satisfactory, exhibiting reversibility and improved specific capacity. Furthermore, the SnSb: Ni, Fe matrix exhibits a high electrical conductivity of 9.27 × 10−4 S cm−1 at room temperature, indicating improved anodic properties.

A lifetime assessment and prediction method for large area solder joints

Mechanical bending fatigue experiments were conducted on large area Pb-rich and SnSb-based model solder joints consisting of Cu-strip/solder/DCB substrates. Experimental lifetime curves in the range between 105 and 108 loading cycles at room and elevated temperature showed an improved fatigue resistance for SnSb alloys. Crack length as a function of loading cycles (da/dN) was determined for selected samples to study the cyclic degradation behaviour of the solder layer. Crack initiation and propagation in the joints was modelled on the basis of a damage accumulation rule considering the strain rate and temperature dependency of the solder alloy. Application of the FEM model to large area solder joints allowed calculation of the incremental advancement of the crack front, determination of the crack growth rate (da/dN) and prediction of lifetime under a given loading condition.

Role of Cu, Ti and Ce dopants in SnSb matrix as Li-ion battery anodes

Addition of redox active/ inactive dopants often promotes the battery performance of any anode material. In this research work, we report the tin antimony (SnSb) alloy anodes included with three different dopants viz. Cu, Ti and Ce. The relative performances of these three different alloys have been systematically analyzed and reported. The electrochemical studies carried out by cyclic voltammetry analysis exhibit amplified redox activity and better reversibility of doped samples compared to the pristine. The specific capacitance values for 50 cycles are found to be in the range of 34 mAhg−1, 52 mAhg−1, 47 mAhg−1 and 65 mAhg−1 when tested with aqueous LiNO3 electrolyte solution for the pristine, Cu, Ti and Ce doped SnSb alloys respectively. The room temperature AC Impedance analyses of these samples reveal the augmented electrical conductivities of the doped samples. Overall, SnSb: Cu and SnSb: Ce samples are found to offer better anodic properties compared to the other samples.