Tin Anode Research Articles

Oxidation leaching of tin anode slime by controlling potential

The selective leaching of tin anode slime was extremely important in the process of the recovery of tin anode slime. With the successful leaching, the efficiency of value metals recycling was elevated obviously. Hence, the pretreatment of tin anode slime was studied in this paper by using the environmental technology and hydrometallurgical approach to achieve the goal of valuable metal recovery from traditional waste tin anode slime. It is worth noting that there are a large amount of value metals including Sn, Sb, Bi, Cu and Ag in the tin anode slime. The results indicated the optimal conditions of leaching process are 3.0 M HCl with 0.1M NaClO3 and liquid-solid mass ratio of 30 ml/g in 30 minutes at 45 degrees of Celsius and about Sn 85.32%, Sb 96.93%, Bi 97.63%. Meanwhile, silver and copper were all leached out by HCl solution in the leaching of tin anode slime.

Innovative methodology for comprehensive use of tin anode slime: Preparation of CaSnO3

Tin anode slime, a secondary resource containing Sn, was used as a raw material in the preparation of CaSnO3 via the processes of soda roasting, alkaline leaching, and precipitation. The effects of roasting, leaching, and precipitation on the extraction of tin from slime were investigated in detail. The following optimum conditions were identified: Na2CO3/tin anode slime mass ratio of 1:1, roasting temperature of 1000 °C, roasting time of 45 min, charcoal powder dosage of 20%, NaOH concentration of 2 mol/L, liquid-to-solid ratio of 14:1, leaching temperature of 65 °C, leaching time of 90 min, CaO/Sn mole ratio of 3.5:1, precipitation temperature of 85 °C, and precipitation time of 120 min. Under these conditions, more than 95% of Sn was extracted from tin anode slime after roasting and leaching, in which Sn was converted into Na2SnO3, which enhanced Sn extraction. Furthermore, more than 99% of Sn was precipitated from the leach solution via the reaction with CaO. The proposed method exhibits advantages of low pollution, low cost, and high leaching rate, when compared with the conventional preparation of CaSnO3 or treatment of tin anode slime.

Si–TiN alloy Li-ion battery anode materials prepared by reactive N2 gas milling

Si–TiN alloys were prepared by reactive gas mechanical milling of Si and Ti powders in N2(g) for use as anode materials in Li-ion cells. This is a low-cost and simple method to prepare Si–TiN anode materials. As a comparison, Si–TiN alloys were also synthesized more conventionally by ball milling Si and TiN powders in Ar. Both Si–TiN alloys have similar phase compositions, however the Si–TiN alloys prepared by N2 reactive gas milling have a more homogenous TiN distribution at the nanometer-scale. As a consequence, Si–TiN alloys prepared by N2 reactive gas milling where much more resistant to Li15Si4 formation during cycling in Li-cells, resulting in improved cell performance.

Hierarchical Sulfur-Doped Graphene Foam Embedded with Sn Nanoparticles for Superior Lithium Storage in LiFSI-Based Electrolyte.

Lithium-ion batteries based on tin (Sn) anode have the advantage of high energy density at a reasonable cost. However, their commercialization suffers from rapid capacity fading caused by active material aggregation, huge volumetric change, and continuous formation/deformation of solid-electrolyte interphase (SEI). Herein, we report an anode made of nanosized metallic Sn particles embedded in a hierarchically porous sulfur-doped graphene foam (Sn@3DSG). In this design, the sulfur-doped graphene foam provides abundant active defect sites to facilitate the rapid lithium-ion diffusion from outside to inside the Sn nanoparticles. Meanwhile, the hierarchical pores resulting from the self-assembly of graphene and evaporation of nanosized metallic Zn provide sufficient space to hold the volumetric changes of Sn. Owing to these merits, the as-prepared Sn electrode exhibits an excellent lithiated capacity (1272 mA h g-1 at 200 mA g-1) and high-rate performance (345 mA h g-1 at 2000 mA g-1) in the LiFSI-based electrolyte. It is also discovered that a LiF-Li3N-rich SEI layer is formed on the surface of the Sn electrode in a LiFSI-based electrolyte, which is beneficial for enhancing the electrode's cycling stability. Our work shows great promise of composite Sn anodes for future high-energy-density lithium-ion batteries.

Synchronized electrospinning and electrospraying technique for manufacturing of all-solid-state lithium-ion batteries

The complexity and expense of manufacturing all-solid-state batteries have long hindered the development of large-scale all-solid-state batteries for transportation and grid storage applications. Key issues include electrolyte-electrode interfacial resistance, air and moisture stability, and mass production capabilities. In this work, we propose a new battery manufacturing method which overcomes the challenges in interfacial resistance and scalability by using synchronized electrospinning and electrospraying. This method enables layer-by-layer depositing of cathode, solid-state electrolyte, and anode layers directly on top of one another. Herein, a LiFePO4 cathode and a Tin (Sn) anode have been selected to create for the first time a proof of concept all-solid-state lithium-ion battery in a full-cell configuration by using the synchronized electrospinning and electrospraying technique. This electrospinning and electrospraying synchronized technique created a poly(ethylene oxide)-based electrolyte, which demonstrates a conductivity of ∼1⋅10−5 at room temperature and ∼1⋅10−3 S cm−1 at 60 °C. Using the air-stable electrolyte and electrode materials, the synchronized electrospinning and electrospraying technique enables manufacturing of all-solid-state batteries in an ambient environment with reversible electrodes outlined in this work. Furthermore, the approach could ensure a straightforward transition to a roll-to-roll process and incorporate a wide range of materials for future large-scale manufacturing.

Characterization of dynamic morphological changes of tin anode electrode during (de)lithiation processes using in operando synchrotron transmission X-ray microscopy

The morphological evolution of tin particles with different sizes during the first lithiation and delithiation processes has been visualized by an in operando synchrotron transmission X-ray microscope (TXM). The in operando lithium ion battery cell was operated at constant current condition during TXM imaging. Two-dimensional projection images with 40 nm resolution showing morphological evolution were obtained and analyzed. The analysis of relative area change shows that the morphology of tin particles with different sizes changed simultaneously. This phenomenon is mainly due to a negative feedback mechanism among tin particles in the battery electrode at a constant current operating condition. For irregular-shaped tin particles, the contour analysis shows that the regions with higher curvature started volume expansion first, and then the entire particle expanded almost homogeneously. This study provides insights for understanding the dynamic morphological change and the particle-particle interactions in high capacity lithium ion battery electrodes.

Temperature-Dependent Characteristics of GaN Schottky Barrier Diodes with TiN and Ni Anodes**Supported by the National Key Research and Development Plan under Grant No 2017YFB0403000, and the Fundamental Research Funds for the Central Universities under Grant No JB181110.

The effect of temperature on the characteristics of gallium nitride (GaN) Schottky barrier diodes (SBDs) with TiN and Ni anodes is evaluated. With increasing the temperature from 25 to 175°C, reduction of the turn-on voltage and increase of the leakage current are observed for both GaN SBDs with TiN and Ni anodes. The performance after thermal treatment shows much better stability for SBDs with TiN anode, while those with Ni anode change due to more interface states. It is found that the leakage currents of the GaN SBDs with TiN anode are in accord with the thermionic emission model whereas those of the GaN SBDs with Ni anode are much higher than the model. The Silvaco TCAD simulation results show that phonon-assisted tunneling caused by interface states may lead to the instability of electrical properties after thermal treatment, which dominates the leakage currents for GaN SBDs with Ni anode. Compared with GaN SBDs with Ni anode, GaN SBDs with TiN anode are beneficial to the application in microwave power rectification fields due to lower turn-on voltage and better thermal stability.

GaN Schottky Barrier Diodes with TiN Electrode for Microwave Power Transmission

In this study, TiN anode GaN Schottky barrier diodes (SBDs) with a low access sheet resistance of 28 Ω/□ were fabricated for microwave power transmission application. The performance of the diodes at room temperature (RT) is comparable with the ideality factor n and Schottky barrier height (SBH) were 1.28 and 0.47 eV for the 8-finger SBDs, 1.22 and 0.49 eV for the 16-finger SBDs, respectively. A low on-resistance of 5.71 and 3.58 Ω were obtained for 8-and 16-finger SBD at RT, respectively. The low series resistance induced by larger anode area of 16-finger SBDs results in a lower turn-on voltage of 0.47 V compared with that of 0.68 V for the 8-finger one. Besides, the temperature dependent current-voltage characteristics demonstrate that the TiN anode has a good temperature stability. And the temperature dependent performance of the 16-finger SBDs present a better uniformity than that of the 8-finger SBDs.

Current Collector Interface for Phase Changing Tin Anode in Sodium Ion Batteries: Insight from First Principles Calculations

Performance of an efficient and high capacity Lithium-ion battery (LIB) and Sodium-ion battery (NIB) greatly depends upon electrode-current collector interface. While copper (Cu) is most extensively used current collector at the anode end, it has been associated with numerous functional issues such as debonding, corrosion, strain accommodation, low flexibility, and high cost and weight. In this work, we investigate the comparative performance of Graphene with Cu as the current collector for NIB anode. Graphene not only provides the battery system much-needed flexibility, cost, and weight efficiency but also imparts mechanical stability to the system during the sodiation and de-sodiation cycles. Tin (Sn) has been taken up as model anode material owing to its potential and promising high theoretical specific capacity of 994 mAh/g. However, the anodic performance of Sn is limited by its high-volume expansion and multiple phase changes which leads to subsequent mechanical failure. Therefore, the effect of mechanical strains and phase transitions during battery performance on the interface has been investigated in detail. We have employed vdW inclusive GGA based Density Functional Theory (DFT) implemented in VASP to study the effect of sodiation and de-sodiation on the mechanical integrity of anode and current collector interface. We report that Graphene is more efficient in combatting mechanical stresses generated in the anode during the performance and also allows easy expansion to Sn. We hope that this work will throw more light on the mechanics and chemistry that are prominent at the interface of an anode and current collector.

3D lithium ion battery fabrication via scalable stacked multilayer electrodeposition

This study focuses on the creation of 3D full cell lithium ion batteries via a multilayer stacked electrode approach. The electrodepositon based processes enable individual, deterministic control of all cell dimensions, and thus allow for tunable total energy outputs while maintaining excellent intrinsic performance. Incorporation of electrodeposited nanoporous lithium manganese oxide cathodes and thin film nickel–tin anodes into a vertically interdigitated multilayer cell enables energy densities of up to 193 Wh l−1 and power densities of up to 1233 W l−1. Additionally, the multilayer fabrication increases device areal and volume scalability over multiple orders of magnitude, resulting in total energy outputs of up to 20 mWh and power outputs of 178 mW.

A high-energy-density sodium-ion full battery based on tin anode

Sodium-ion batteries (SIBs) have been considered as promising candidates for large-scale energy storage, owing to the high abundance and low cost of sodium (Na) resources. However, the development of full SIB has been hindered by low energy density because of the sluggish kinetics of large Na+. Here, we report a full SIB with commercial tin (Sn) anode, cross-linked Na3V2(PO4)3/carbon nanotubes composites (NVP-CNT) cathode, and ether-based electrolyte. Sn is capable of delivering high reversible capacity via formation of Na15Sn4 and stable solid-electrolyte interface (SEI) in initial cycles. Meanwhile, the NASICON-type NVP enables ultrafast and stable Na+ intercalation/extraction, and the incorporation of CNT can improve its electrical conductivity. The assembled full SIB delivers high output voltage of ~3.2 V, high energy density of 253.4 W h kg−1 at 1600 W kg−1 based on total mass of both cathode and anode, and remarkable capacity retention of 96.1% after 180 cycles. These merit construction of high-energy full SIBs and will promote the development of SIBs.

Effect of Auxetic Structure of PVdF on Tin Anode Stability for Na-ion Batteries

Effect of Auxetic Structure of PVdF on Tin Anode Stability for Na-ion Batteries

Neutron radiation on tin anodes of lithium-ion batteries

The operating durability of lithium-ion batteries is a principal problem in universe exploration or rescuing work in the nuclear radiation area. In the study, the neutron irradiation experiments were conducted on film-tin electrodes using the radiation dose of 1011, 1012, 1013 and 1014 n cm−2, respectively. The results show that the particle size grows with the increasing radiation does by atomic force microscopy (AFM) and scanning electron microscope (SEM). In addition, the degressive trend of specific capacity of tin anodes after neutron radiations increases with the increasing radiation dose. The fade of electrochemical performances may be attributed to the increasing particle size and defects induced by neutron radiation.

Synthesis of SnO2 Nanoparticles by Electrooxidation Method and Their Application in Dye-Sensitized Solar Cells: The Influence of the Counterion

A fast and facile electrochemical method called electrooxidation was used to prepare SnO2 nanoparticles. In this route, a sacrificial tin anode is dissolved in an electrolyte by applying a voltage to an electrochemical cell. We used different electrolyte environments, namely tetramethylammonium chloride and different counterions of tetrabutylammonium cation, viz. Br−, Cl−, and ClO 4 − . Characterization results showed that the size distribution was more uniform for the nanoparticles created with Br− and Cl− counterions. Furthermore, the particles in these samples were smaller than in the others. The amount of OH groups on the surface of the Br− and Cl− samples was higher than for the other samples, enhancing dye adsorption. Dye-sensitized solar cells (DSSCs) were fabricated from the produced SnO2 nanoparticles, and the influence of the different counterions on their performance was investigated. By varying the counterion in the electrolyte, samples with different hydrophilic nature and dye-loading ability were obtained. The dye adsorption and consequently the current density of the cell made from the Br− solution were higher than for the other samples, and the power conversion efficiency in this case reached 1.5%.

Freestanding SnO2 films produced with anodic polarization in acidic media containing colloidal tin hydroxides

Abstract Within the scope of the study, we aimed to develop a strategy for production of thick self -supporting tin oxide films with high surface area by anodic oxidation of metallic tin in acidic solutions. This has not been achieved before because of the highly porous and non-adherent nature of the oxidation products and high dissolution rate of tin in acidic solutions. Entrapment of the gelatinous colloidal tin hydroxides in the film during anodic oxidation exerted the necessary effect for decreasing the permeability of the oxide and dissolution of tin. Below this adherent and semi permeable film, a tin ion supersaturated zone was created, enabling the whisker type growth of complex tin oxyhydroxides at the metal/oxide interface. Colloidal +4 valent acid insoluble tin hydroxides are prepared by oxidation of dissolved Sn+2 ions in sulfuric acid solution with H2O2. Moreover by utilizing this approach growing 100–150 μm thick layers was possible, which were easily detached as free standing film from the underlying tin anode. The structure, chemistry and morphology of the films produced by anodic oxidation in acidic solutions were determined by using micro Raman spectroscopy, X-Ray diffraction (XRD) and SEM. Since the films produced by the above stated method consisted of a complex mixture of oxides, hydroxides and sulfates, annealing treatment was applied to convert these structures into stoichiometric SnO2.

Temperature sensor using thermally stable TiN anode GaN Schottky barrier diode for high power device application

The characteristics of GaN Schottky barrier diodes fabricated with TiN and Ni anodes were evaluated in the temperature range from 25 to 175 °C. The Schottky barrier height (ideality factor) increases (decreases) with increasing temperature for both kinds of diodes owing to the barrier height being nonhomogeneous. The GaN diode with TiN anode presents better interface quality and thermal stability is adopted for temperature sensing application. It demonstrated that the sensitivity of the TiN diode is approximately 1 mV/K and varies only slightly for all current levels.

Analysis of Interfacial Processes at Tin Anodes Using in situ Enhanced Raman Spectroscopy (SHINERS) and Advanced Electrochemical Techniques

As Li-ion batteries (LiBs) have become on one of the most reliable power sources, new electrode materials with higher lithium-retention capacity such as tin and silicon-based anodes as well as high voltage oxide or polyanion-type cathodes materials already stand as promising candidates to address the growing need of inexpensive, efficient energy storage systems for the forthcoming energy transition. Despite their initial promising capacity, continuous cycling ineluctably leads to a fading of their performances. The comprehension of failure mechanisms during operation will pave new routes for the design of battery electrode and electrolytes. This work focusses on the study of interfacial processes at tin anodes, specifically on the dynamics of formation and composition of the solid electrolyte interphase upon cycling. The strategy proposed herein consists in associating enhanced Raman spectroscopy and advanced electrochemistry techniques derived from electrochemical impedance techniques (Quart crystal microbalance and AC electrogravimetry). We report the compositional study of the SEI (1) by SHINERS using the plasmon resonance of gold nanoparticles which enhances the Raman signal of the compounds in close vicinity and compensates for the low Raman scattering cross section of the compounds forming the SEI (2). Using SHINs on tin electrodes, Raman signature of the SEI were successfully extracted ex-situ but also in situ through the electrolyte. Composition data are compared to structural information of the SEI extracted by EQCM (3,4). Influence of the electrolyte composition on the SEI properties will be detailed during the presentation.

Environmentally friendly recycling of SnO2/Sn3O4 from tin anode slime for application in formaldehyde sensing material by Ag/Ag2O modification

Tin anode slime, a by-product of the tin plating process composed mainly of tin oxides, offers great potential for application to the field of gas sensing. In the present study, Ag-doped SnO2/Sn3O4 materials with excellent sensing properties to formaldehyde (HCHO) gas were successfully obtained by combining a simple pre-treatment method with a dipping process. The performance of the modified SnO2/Sn3O4 sensing material was systemically studied by varying the Ag-dopant content. The results indicated that the sensing properties of the SnO2/Sn3O4 material to HCHO were greatly improved compared to the pristine material, depending strongly on the Ag-doping content. The optimum sensing material, 2 mol% Ag/Ag2O-doped SnO2/Sn3O4, exhibited good sensing properties including a high response (12.76) to 100 ppm HCHO at a low operating temperature (160 °C) as well as a rapid response/recovery speed (5 s/5 s). The selectivity toward HCHO was also enhanced by the assistance of Ag nanoparticles. Importantly, the recovery of tin oxides from tin anode slime represents a resource-saving and environmentally friendly development.

Electrochemical behavior of tin anode in ascorbic acid solutions

The anodic behavior of tin in ascorbic acid (AA) solutions was investigated using cyclic and/or linear sweep voltammetry and chronopotentiometry method and complemented by XRD and SEM examination. The results showed that the cyclic voltammetric curves in 0.5 M ascorbic acid at 18 ± 0.5 °C involves active/passive transition followed by pitting corrosion. In the active region, Sn dissolves as Sn2+ and Sn4+ and dissolution process is under diffusion control. Passivation is due to deposition of Sn(OH)4 and/or SnO2 on the electrode surface. Pitting corrosion is attributed to local dissolution of the passive film by the adsorbed AA molecules and initiating of pitting attack at a pitting potential Eb. Increasing the acid concentration and temperature enhances the anodic dissolution and shifts Eb to more active direction. Addition of Cl−, Br− and I− in AA enhances both the anodic dissolution and pitting corrosion of Sn. The extent of enhancements depends upon the type and concentration of halide added. The chronopotentiometry curves at constant current densities revealed that increasing the imposed current density decreases the time needed to passivation tp. Addition of low concentrations of Cl−(<5 × 10−5 M) in 0.5 M AA induces pitting corrosion while higher concentrations of Cl− prevent the passivation and the electrode remains in its active state.

Effect of sodium salts on the cycling performance of tin anode in sodium ion batteries

To determine the effect of electrolyte salts on the cycling properties of tin anodes in sodium ion batteries, sodium/tin cells were prepared using eight electrolytes containing NaCF3SO3, NaBF4, NaClO4, and NaPF6 in ethylene carbonate-dimethyl carbonate (EC-DMC) and EC-DMC/fluoroethylene carbonate (FEC) solvents. The first charge capacity and cycling properties strongly depended on the electrolyte salts. Additionally, an appropriately chosen electrolyte salt in combination with the FEC additive improved the cycling properties of the tin electrode. The tin electrode in the presence of the FEC-containing NaPF6-based electrolyte exhibited the best cycling properties. The first charge capacity and charge capacity after the 45th cycle were 220 and 189 mAh g−1 electrode, respectively at a current density of 84.7 mA g−1 electrode. The rate performance is also studied using the optimized electrolyte which reveals the ability of the electrode to perform in high current application. At a high current density of 4235 mA g−1 electrode, the capacity delivered is 24 mAh g−1 electrode. At a current rate of 1694 mA g−1 electrode, at the end of 1400th cycle, capacity is about 45 mAh g−1 electrode. The results of the study clearly indicate that the electrolyte salts critically affect the electrochemical performance of the tin anode in sodium ion batteries.