Tin Materials Research Articles

First-Principles Study on Lithiation Process of Sio Anode for Li-Ion Batteries

Lithium-ion secondary batteries (LIB) with a high energy density have been developed mainly for use in small mobile devices. In recent years, the high capacity of LIB has become important for automobile applications. One possible high-energy density solution is the use of high-capacity negative electrodes fabricated from tin, silicon, or other materials, and a-SiO materials have been already commercialized. However, a-SiO materials has the issue of capacity degradation during charge-discharge cycles. In particular, it is speculated that the structural change during charging process causes the capacity degradation, but the detail has not been clarified yet. Therefore, in this study, we clarify the local structural changes in a-SiO up to full charge using first-principles calculations.In our previous study [1], a-SiO models were generated using classical molecular dynamics (MD) simulations with neural network potentials.Using one of these models, we explore the lithiation process of a-SiO using first-principles calculations with SIESTA code [2]. The simplest method to obtain a-Li x SiO model is to melt an initial structure in which Li atoms are randomly arranged at high temperature and then cool it. But it was found that this process could not reproduce the actual charge process and Li atoms should be placed at stable sites. Therefore, we developed a computational code with which stable sites of Li atoms can be searched efficiently using Bayesian optimization.Fig. 1 shows Li-inserted models at (a) 0%, (b) 55% and (c) 100% SoC (State of Charge). Li atoms are gradually inserted into the SiOx phase in the initial state of charging, and inserted into the Si phase over 20% SoC. These results are consistent with previous experimental results [3]. One Li6O octahedron can be seen in the model at 55% SoC, and the number of Li6O octahedra increases to five in the model at 100% SoC. The formation of Li6O octahedra during charging is irreversible, which is considered to cause the capacity degradation. To prevent capacity degradation, it is necessary to suppress the formation of these structures.

Improved SERS activity of TiN microstructures by surface modification with Au

Over the years, numerous outstanding research groups around the world have been working tirelessly on metallic SERS substrates. Although these efforts have led to the development of various sensors and pushed the field forward, today this line of research seems saturated and exhausted. In this work, we address this issue by exploring an emerging topic in recent literature: the fabrication of high-performance TiN SERS-active structures. TiN thin film was sputtered onto pyramidal Si microstructures. Spectroscopic ellipsometry measurements confirmed the plasmonic properties of the TiN material above its plasma wavelength of 515 nm. The Si-TiN surface was subsequently modified with an Au layer, which was then transformed into Au nanoparticles (Au NPs) during the Rapid Thermal Annealing process. The Si-TiN-AuNPs samples exhibited the highest extinction intensity, as well as the best SERS signal intensity for the model Raman reporter molecule. Further analysis of the SERS data showed that the presence of the Au thin film only moderately increased SERS activity, while Au NPs enhanced the SERS signal by one order of magnitude. Final Si-TiN-AuNPs platforms were successfully employed for the detection of vitamin B12, demonstrating a low limit of detection (8.57•10–8 M) along with excellent point-to-point repeatability.Graphical abstract

Study on the Erosion Resistance of Different TiN Crystal Planes by Molecular Dynamics.

In this study, we innovatively combined the Fe-Ti-N potential function file to construct simulation models of different crystal facets of TiN/Fe ((001), (110), and (111)), which had not been previously explored. Employing molecular dynamics (MD) simulations, the research investigates the microscale differences in erosion resistance and surface properties of various TiN crystal planes under continuous impacts at varying velocities and angles. The results indicate that both surface wear and internal defects of the model increase with the impact velocity. Both TiN(110) and TiN(111) exhibit damage on their surfaces and interiors, with a larger wear range. In contrast, TiN(001), due to its superior elastic recovery capability, maintains a better surface condition, showing significantly less wear compared to TiN(110) and TiN(111). This disparity in performance among different crystal planes is attributed to variations in molecular gaps between planes, bonding points within the lattice, types of forces, and modes of action. Further research revealed that the wear volume increased with the rise in impact angle, reaching its peak at 90°. Regardless of the impact angle, TiN(001) consistently outperformed TiN(110) and TiN(111). The aim of the research is to compare the surface and internal defects of different crystal facets at the microscopic level, thereby selecting superior crystal facets and providing theoretical reference for the application of TiN materials in practical fracturing environments.

A sheet-like tin-based metal-organic framework with enhanced lithium storage.

A novel sheet-like tin-based metal-organic framework exhibited a specific capacity for lithium storage as high as 1033.3 mAh g-1 at 200 mA g-1 with excellent cycling stability. This framework, due to its unique porous structure and multiple lithium storage sites, could better cope with challenges occurring during lithium insertion/extraction than could traditional tin materials.

Optimization of garnet-type solid-state lithium batteries via synergistic integration of an advanced composite interface for elevated performance

Solid-state batteries (SSBs) represent a pivotal avenue of development owing to their superior energy density and enhanced safety profile. However, the widespread utilization about SSBs confronts challenges such as inadequate interfacial connectivity resulting in high resistance, dendrite formation, and volumetric fluctuations in the lithium metal anode during plating and stripping. In this study, we introduce an innovative and remarkably efficient approach, leveraging the transformative potential of TiN-induced conversion. This method yields a lithium-ion-conductive TiN material concurrently addressing pre-existing porosity. The LiTiN| LLZTO| LiTiN symmetric cell is particularly noteworthy for its remarkable long-term cycle stability, which exceeds 1000 h at 0.2 mA cm−2, and its remarkable critical current density of 1.4 mA cm−2 at 25 °C. By subjecting TiN, the formation of the Li-Ti-N phase is induced, thereby establishing an additional Li3N-conductive layer that significantly enhances battery performance. Of paramount significance is the validation of the exceptional attributes of the composite through the deployment of LiFePO4 (LFP) full cells. In this configuration, the LFP coupled full cell manifests a remarkable discharge rate capacity of about 147 mAh g−1 at 1C, along with a noteworthy discharge capacity retention rate of 90 % even following 1000 charge and discharge cycles. These outcomes underscore the material’s robust lithium affinity and uniform lithium-ion distribution, which together mitigate dendrite growth and enhance the cycle stability of lithium-metal batteries.

Electrodeposition of Tin and Antimony-Based Anode Materials for Sodium-Ion Batteries

Tin antimonide (SnSb) is a promising alloying anode for sodium-ion batteries due to its high theoretical capacity and relative stability. The material is popular in the battery field, but, to our knowledge, few studies have been conducted on the influence of altering Sn and Sb stoichiometry on anode capacity retention and efficiency over time. Here, Sn-Sb electrodes were synthesized with compositional control by optimizing electrodeposition parameters and stoichiometry in solution and the alloys were cycled in sodium-ion half-cells to investigate the effects of stoichiometry on both performance and electrochemical phenomena. Higher concentrations of antimony deposited into the films were found to best maintain specific capacity over 270 cycles in the tin-antimony alloys, with each cell showing a slow, gradual decrease in capacity. We identified that a 1:3 ratio of Sn:Sb retained a specific capacity of 486 mAh g−1 after 270 cycles, highlighting a need to explore this material further. These results demonstrate how control over stoichiometry in Sn-Sb electrodes is a viable method for tuning performance.

Ultra-broadband, high-efficiency metamaterial absorber based on particle swarm optimization algorithm

In this study, we propose an ultra-broadband, high-efficiency absorber based on the particle swarm optimization (PSO) algorithm. By coupling multi-layer planar structures with pyramid structures and optimizing structural parameters using code, the absorber can achieve efficient absorption in the ultra-broadband band. According to the simulation results, the average absorptance of the absorber exceeded 99.98% in the wavelength range from 300 nm to 2000 nm. Due to the gradual geometric structure of the pyramid, excellent anti-reflection ability can be achieved, and it has a high degree of symmetry, making the absorber insensitive to the incident angle and polarization state. The simulation results also show that the absorption efficiency can reach more than 90% when the incidence angle varies from 0° to 60°. Due to the high thermal and chemical stability of SiO2, Ti, and TiN materials, the absorber can be used in a wider range of fields. This study not only proposes an efficient absorption structure, but also provides an idea for the design optimization of absorbers.

MAX Phase Ti2AlN for HfO2 Memristors with Ultra‐Low Reset Current Density and Large On/Off Ratio

AbstractA Ti2AlN MAX phase layered thin film electrode and oxygen getter layer for HfO2‐based two‐terminal memristors is presented. The Ti2AlN/HfOx/Ti memristor devices exhibit enhanced resistive switching performance, including an ultra‐low reset current density (< 10−8 MΩ cm2), substantial on‐off ratio (≈ 6000), excellent multi‐level functionality (≈ 9 distinct states), impressive retention (up to 300 °C), and robust endurance (>200 million) as compared to conventional TiN and other alternative materials based memristors. Experimental measurements and modeling suggest that the distinctive combination of low thermal conductivity, high electrical conductivity, and unique ultra‐thin layer‐by‐layer structure of the Ti2AlN MAX phase thin film contribute to this exceptional performance with good reproducibility and stability. The results demonstrate for the first‐time the potential of this innovative sputtered MAX phase material for engineering energy‐efficient, high‐density non‐volatile digital, and analog memory devices aimed toward next‐generation sustainable artificial intelligence.

Nanostructure Engineering of Alloy-Based Anode Materials with Different Dimensions for Sodium/Potassium Storage

Sodium/potassium-ion batteries have drawn intensive investigation interest from researchers owing to their abundant element resources and significant cost advantages. Anode materials based on alloy reaction mechanisms have the prominent merits of a suitable reaction potential and high theoretical specific capacity and energy density. However, very large volumetric stresses and volume changes during the charge/discharge process and the resulting electrode structural cracking, deactivation and capacity fading seriously hinder their development. To date, a series of modification strategies have been proposed to tackle these challenges and achieve good electrochemical performance. Herein, we review the recent advances in the structural engineering of alloy-type anodes for sodium/potassium storage, mainly including phosphorus, tin, antimony, bismuth and related alloy materials, from the perspective of dimensional structure. Furthermore, some future research directions and unresolved issues are presented for the investigation of alloy-based anode materials. It is hoped that this review can serve as a guide for the future development and practical application of sodium/potassium-ion batteries.

High-Pressure Calibration TiN Equation of State

High pressure is becoming an interesting area of research for originating vital properties in crystalline solids. In the present study, the pressure equation of the state of TiN was investigated by employing various equations of state (EoS) presented in the literature, such as Dodson EoS, Barden EOS, Birch-Murnaghan (B-M) EoS. The EoSs were processed to find the high-pressure effects on the characterizations of TiN such as volume compression ratio, bulk modulus B, Grüneisen parameter, and phonon frequency spectrum. It was shown that a gigantic pressure results in a significant reduction in the volume of the TiN material, and the volume compression ratio reduction, is almost the same for the existing equations of state and the comparative literature results up to a pressure of 80 GPa. The maximum pressure difference is observed to be 4.85 GPa. over the entire pressure of 120GPa. Increasing the bulk modulus with high pressure was expected by the present EoSs, and up to the pressure of about 60 GPa, all curves of bulk modulus are matched with each other. Eventually, a fair comparison has been made between the present results and the first principle approximation along with the generalized gradient approximation method in which a perfect agreement was observed. Finally, the feasibility of TiN EoS as a standard pressure calibration was demonstrated.

Design of an Ultra-Wideband Transparent Wave Absorber.

In this paper, a multilayer ultra-wideband transparent metamaterial wave absorber is proposed, which has the characteristics of ultra-wideband wave absorption, light transmission and flexible bending; in addition, due to the complete symmetry of the structure, the absorber has polarization insensitivity to incident electromagnetic waves. Both simulation and experimental results show that the frequency range of the microwave absorption rate is higher than 90% between 8.7 GHz and 38.9 GHz (between which most of the absorption rate can reach more than 95%), the total bandwidth is 30.2 GHz, and the relative bandwidth is 126.9%, realizing microwave broadband absorption and covering commonly used communication frequency bands such as X-band, Ku-band, and K-band. A sample was processed and tested. The test results are in good agreement with the results of the theoretical analysis, which proves the correctness of the theoretical analysis. In addition, through the selection and oxidation of indium tin (ITO) materials, the metamaterial also has the characteristics of optical transparency and flexibility, so it has potential application value in the window radar stealth and conformal radar stealth of weapons and equipment.

LCA and C-LCC Indicator as Tools for Sodium-Ion Batteries’ Eco-Design

Sodium-ion batteries are considered promising alternatives to lithium-ion technology; however, the diffusion on a commercial scale is hindered by the struggle to identify materials with high electrochemical performances. Studies available in the literature are mainly focused on electrochemical performance and neglect aspects related to the environmental sustainability. In fact, the current state-of-the-art (presented in this study) shows that life cycle assessment (LCA) studies related to the production processes of electrode materials for Na-ion batteries are still very limited. The LCA methodology applied during the development of a technology phase can constitute a valid support for an eco-oriented design and, therefore, to the choice of solutions characterized by a lower environmental impact with the same electrochemical performance. In this context, a life cycle-based environmental–economic assessment was performed to evaluate the environmental impacts of the production process of cathode and anode materials for sodium-ion batteries. The study is focused on the cathodic active material Na0.66MnO2, considering two synthesis paths, and the anodic material consisting of tin (Sn) and Sn-carbon nanofiber (Sn-Cn) active material, binder, and other additives. Results illustrate the environmental performance of the different materials and constitute a useful input for their selection within an eco-design view.

An Analysis of Income Sources and Food Security Status in Haor Regions of Kishoregonj District, Bangladesh

This study aims to investigate income diversity and food security status among people living in the Haor area, with the objective of informing development policies for these regions. The research focused on assessing the socioeconomic characteristics, income diversity, and food security status of 120 randomly selected households in the Nikli and Tarail upazilas within Kishoregonj district, Bangladesh. Data was gathered through direct face-to-face interviews. The study revealed that the majority of households (91.66%) were male-headed, with an average family size of 5.10 members. A significant proportion (62.5%) of respondents fell within the 30-64 age group. Education-wise, a substantial portion (39.16%) of respondents had a secondary level of education, while 25% were employed in the agriculture sector. Approximately 45.83% of households were constructed with tin materials. The average monthly income and expenditure were Tk. 9536 and Tk. 8316, respectively. Income diversification was found to be prevalent among the respondents; however, within individual households, diversification was limited. The Simpson's and Shannon's indices of diversity for income were 0.84 and 0.88, respectively. About 25% of households were classified as ultra-poor, 29.17% as hard-core poor, and 20.83% were in the category of absolute poverty. On the positive side, 25% of the sample households were deemed non-poor. These findings underscore the urgent need for policy changes to address poverty eradication and enhance the standard of living in the study area. By understanding the socioeconomic dynamics and food security challenges faced by Haor communities, policymakers can devise targeted interventions to uplift the living conditions and well-being of the residents in these regions.

Activation Energy and Bipolar Switching Properties for the Co-Sputtering of ITOX:SiO2 Thin Films on Resistive Random Access Memory Devices.

Activation energy, bipolar resistance switching behavior, and the electrical conduction transport properties of ITOX:SiO2 thin film resistive random access memory (RRAM) devices were observed and discussed. The ITOX:SiO2 thin films were prepared using a co-sputtering deposition method on the TiN/Si substrate. For the RRAM device structure fabrication, an Al/ITOX:SiO2/TiN/Si structure was prepared by using aluminum for the top electrode and a TiN material for the bottom electrode. In addition, grain growth, defect reduction, and RRAM device performance of the ITOX:SiO2 thin film for the various oxygen gas flow conditions were observed and described. Based on the I-V curve measurements of the RRAM devices, the turn on-off ratio and the bipolar resistance switching properties of the Al/ITOX:SiO2/TiN/Si RRAM devices in the set and reset states were also obtained. At low operating voltages and high resistance values, the conductance mechanism exhibits hopping conduction mechanisms for set states. Moreover, at high operating voltages, the conductance mechanism behaves as an ohmic conduction current mechanism. Finally, the Al/ITOX:SiO2/TiN/Si RRAM devices demonstrated memory window properties, bipolar resistance switching behavior, and nonvolatile characteristics for next-generation nonvolatile memory applications.

Extended-SWIR GeSn LEDs with Reduced Footprint and Efficient Operation Power

Complementary metal oxide semiconductor-compatible short- and midwave infrared emitters are highly coveted for the monolithic integration of silicon-based photonic and electronic integrated circuits to serve a myriad of applications in sensing and communication. In this regard, the group IV germanium–tin (GeSn) material epitaxially grown on silicon (Si) emerges as a promising platform to implement tunable infrared light emitters. Indeed, upon increasing the Sn content, the bandgap of GeSn narrows and becomes direct, making this material system suitable for developing an efficient silicon-compatible emitter. With this perspective, microbridge PIN GeSn LEDs with a small footprint of 1520 μm2 are demonstrated, and their operation performance is investigated. The spectral analysis of the electroluminescence emission exhibits a peak at 2.31 μm, and it red-shifts slightly as the driving current increases. It is found that the microbridge LED operates at a dissipated power as low as 10.8 W at room temperature and just 3 W at 80 K. This demonstrated low operation power is comparable to that reported for LEDs having a significantly larger footprint reaching 106 μm2. The efficient thermal dissipation of the current design helped reduce the heat-induced optical losses, thus enhancing light emission. Further performance improvements are envisioned through thermal and optical simulations of the microbridge design. These simulations indicate that the use of GeSn-on-insulator substrate for developing a similar microbridge device is expected to improve the optical confinement toward the realization of electrically driven GeSn lasers.

Influence of Element Lead (Pb) Content in Tin Plating on Tin Whisker Initiation/Growth

The implementation of the Restriction of Hazardous Substances (RoHS) European Union (EU) Directive in 2005 resulted in the introduction of pure tin as an acceptable surface finish for printed circuit boards and component terminations. A drawback of pure tin surface finishes is the potential to form tin whiskers. Tin whiskers are a metallurgical phenomenon that is associated with tin rich/pure tin materials and has been a topic of intense industry interest. The acceptance and usage of pure tin by the electronics industry component fabricators is understandable as the pure tin surface finishes are inexpensive, are simple plating systems to operate and have reasonable solderability characteristics. However, high performance/harsh environment electronics typically have product life cycles that are measured in decades and therefore are much more susceptible to the potential long term threat of tin whiskers. The GEIA-STD-0005-2 “Standard for Mitigating the Effects of Tin Whiskers in Aerospace and High Performance Electronic Systems” established the definition of the term “Pb-free tin” as : “Pb-free Tin is defined to be pure tin or any tin alloy with <3% lead (Pb) content by weight. A functional definition of “pure tin” was necessary so that the electronics industry could establish tin whisker risk protocols against a known acceptable target value in terms of soldering materials and processes. An investigation was conducted to determine the influence of 1% - 5% elemental lead (Pb) content in tin plating on tin whisker initiation and growth. The investigation results were used in the revision of the GEIA-STD-0005-2 “Standard for Mitigating the Effects of Tin Whiskers in Aerospace and High Performance Electronic Systems” specification technical discussions.

Experimental Study on Electro-Spark Additive/Subtractive Repair for Worn Cemented Carbide

Worn cemented carbide tool bits are often discarded because of the difficulty of their repair, resulting in a great deal of waste. Surface strengthening technology often extends the service life of worn tools. Electro-spark deposition (ESD) coating and matrix materials are metallurgically and closely bonded, and the approach has the characteristics of small heat input, a small heat-affected zone, and low repair cost, so it is suitable for strengthening the surface of cemented carbide tools. As the surface of cemented carbide tools is often not flat, which affects the uniformity of the deposited layer, the surface needs to be polished before ESD. Therefore, this paper proposed a method involving the electro-spark additive and subtractive repair of worn cemented carbide. Experiments involving the ultrasonic-assisted EDM grinding (UEDG) of cemented carbide were carried out. The effect of brass, 45 steel, and tungsten electrode materials on the removal rate, tool wear, and surface roughness were investigated. The results showed that the material removal rate of the tungsten electrode could reach 3.27 mm3/min, while the electrode loss was only 8.16%, and the average surface roughness was only 2.465 μm, which was better than the other two electrodes. Thus, the tungsten electrode exhibited a high material removal rate, low electrode loss, and good surface quality. The effects of the TiC, TiN, and TC4 electrodes on cemented carbide ESD were studied using optical 3D surface topography and other instruments, and the surface roughness, thickness, and hardness of the deposited layer were compared. The results showed that the surface roughness of the TC4 material reached 52.726 μm, which was better than that of the TiN and TiC materials. The thickness of the TiC deposition layer was 172.409 μm and the hardness value was 2231.9 HV; thus, the thickness and hardness of the TiC material’s sedimentary layer were better than those of the TiN and TC4 materials.

Enhanced ultra high frequency EMI shielding with controlled ITO nano-branch width via different tin material types.

The development of technologies for electromagnetic wave contamination has garnered attention. Among the various electromagnetic wave frequencies, for high frequencies such as those in the K and Ka ranges, there is a limitation of using only the properties of a single material. Therefore, it is necessary to improve the absorption coefficients by increasing the path of electromagnetic waves through internal scattering at an interface or a structure inside the material. Here, we accurately demonstrated the role of Sn in the growth of an indium tin oxide (ITO) nano-branch structure and grew high-density ITO nano-branches with the lowest thickness possible. Consequently, we obtained shielding efficiencies of 21.09 dB (K band) and 17.81 dB (Ka band) for a film with a thickness of 0.00364 mm. Owing to the significantly high specific shielding efficiency and low thickness and weight, it is expected to be applied in various fields.

Synergistic effect of carbon-decorated hollow TiN architecture for boosting oxygen reduction reaction activity and durability

The development of low-cost and high-efficient electrocatalysts for oxygen reduction reaction (ORR) is a severe challenge for the commercial application of fuel cells. Herein, a durable acidic ORR electrocatalyst composed of carbon nanoparticles decorated on a mesoporous structure of TiN hollow spheres (H-TiN/NC-x) is fabricated for the first time through a hydrothermal-calcination strategy. By moderately adjusting carbon content, the H-TiN/NC-1.00 catalyst exhibits remarkable ORR performance in 0.1 M HClO4 electrolyte with a half-wave potential of 0.80 V, which is close to commercial Pt/C catalyst (0.83 V). Meanwhile, the catalyst reveals a high selectivity for the four-electron pathway with lower H2O2 yield (7 %) and superior tolerance ability to methanol crossover. More importantly, the H-TiN/NC-1.00 catalyst exhibits a higher stability with negligible activity decay than Pt/C catalyst (ΔE1/2 = −80 mV) after 10,000 potential cycles. This outstanding ORR performance for H-TiN/NC-1.00 is attributed to the synergistic effect of unique hollow nanostructure and multiple active sites, which can improve electron transfer and ion diffusion/penetration, maintain the structural stability of hollow spheres for exposing more active sites (H-TiN and NC). Our work demonstrates that manipulating surface state and composition of TiN material is a superior method for optimizing ORR performance in fuel cells applications.

Biomimetic liquid infused surface based on nano-porous array: Corrosion resistance for tin metal and self-healing property

Tin material corrosion has been recognized as an important problem for electronic products. Biomimetics strategies have been adopted to develop intriguing materials to combat corrosion. In this paper, by anodic oxidation, mussel inspired dopamine hydrochloride modification and thiol grafting, lotus leaf inspired superhydrophobic surface (SHS) based on porous SnO2 coating is prepared on tin. Further, a stable liquid infused surface (LIS) enlightened by Nepenthes plant is formed by infusing dimethyl silicone oil into SHS. The wettability, microstructure and chemical composition of tin surface with different modification are characterized by contact angle, scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS) and so forth. The porous SnO2 structure endows superhydrophobicity with a contact angle up to 155.9°. The corrosion resistance of SHS and LIS coating is revealed by scanning Kelvin probe (SKP), electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization (PDP) curves. Corrosion data show that the prepared LIS exhibits better corrosion resistance than SHS. After being soaked in a representative 3.5 wt% NaCl solution for 180 h, the corrosion inhibition efficiency of LIS maintains 99.6%, which is much better than that of SHS. In addition, when being fold or bent to induce cracks, the LIS shows slight change in corrosion inhibition efficiency, indicating the high tolerance to mechanical torsion. Moreover, in response to externally imposed mechanical scratching, LIS demonstrates good self-healing capability, illustrating the high potential for practical usage.