Silicon Particles Research Articles

Four-dimensional electrochemical impedance spectroscopy: Role of microstructure on corrosion behaviour of Al-Si alloys additive-manufactured by laser powder bed fusion

Four-dimensional (4D) electrochemical impedance spectroscopy was applied to clarify the role of microstructures on the corrosion behaviour of Al-Si alloys additively manufactured by laser powder bed fusion in the immersion of NaCl solution. 3D complex impedance plots, comprising real, imaginary, and time axes, indicate that the impedance increases gradually at initial stage and then does not show apparent time variation. These behaviours, following surface morphology analysis, are strongly related to the remaining fine silicon particles on the surface due to the preferential Al dissolution, which suppress the further dissolution from underlying along with the protective oxide film formation.

Nanoparticle manipulation and sorting by phased modulated interference pattern of Gaussian Evanescent Waves

The utilization of Gaussian Evanescent Waves (GEWs) in particle manipulation provides a three-dimensional force distribution that is significantly high at the vicinity of the surface and exponentially decreases as one moves away, hence enabling 3D particle manipulation, unlike plane waves. By coherently interfering four GEWs in various phase combinations, symmetric evanescent field distributions can be obtained, which allows the manipulation of nanoparticles for many applications. With the simulation we conducted, the dynamics of various-sized spherical silicon particles in a continuously flowing liquid setup have been investigated. We present the optimal phase-delayed configurations for trapping, sorting, separating, and rotating the particles.

In English

Samples of MnOx-Na2WO4/SiO2 based on a mesoporous silica matrix were synthesized using manganese acetate, sodium tungstate, tetraethoxysilane (TEOS) as precursors and cetyltrimethylammonium bromide (CTAB), citric acid and triethanolamine as pore generating agent and characterized by scanning electron microscopy with energy dispersive elemental analysis (SEM/EDS), X-ray diffractometry (XRD), electron magnetic resonance (EMR), N2 adsorption-desorption measurements and tested as a catalyst for the reaction of oxidative condensation of methane (OCM). It is shown that the MnNaW/SiO2 catalyst consists of Mn2O3, MnO2, Na2WO4 and SiO2 phases. The EMR and SEM/EDS data indicate a noticeable effect of the reaction conditions on the surface structure and the distribution of catalytically active components in the catalyst structure. Significant changes in the values of the specific surface area and pore volume of the samples with increasing temperature and duration of the reaction were found (the values of the specific surface area and pore volume, respectively, 116.8 m2/g and 0.590 cm3/g - up to and 46.1 m2/g and 0.232 cm3/g after 15 hours of catalyst operation in the OCM reaction at 800 °C). It has been shown that under the conditions of the OCM reaction, the elemental composition of the surface of the MnOx-Na2WO4/SiO2 catalyst changes, and the degree of change depends on the duration of the OCM reaction. Under the influence of the reaction mixture CH4/O2, the content of Mn and W decreases in the first two hours, and the trend towards a decrease in their amount on the catalyst surface with an increase in the duration of the OCM reaction is generally preserved. A detailed X-ray phase analysis also indicates a change in the phase composition of this catalyst under the influence of the CH4/O2 reaction mixture. It is assumed that under the reaction conditions (700–800 °C) the MnOx-Na2WO4/SiO2 catalyst is silicon dioxide particles basely with the cristabolite structure, the surface of which is coated with molten sodium tungstate containing nanosized particles of MnOx structures activated by sodium ions and WOx.

Investigating the failure mechanism of solid electrolyte interphase in silicon particles from an electrochemical-mechanical coupling perspective

Silicon is considered one of the most promising anode materials owing to its high theoretical energy density, however, the volume expansion/contraction during electrochemical lithiation/delithiation cycles leads to instability of the solid electrolyte interphase (SEI), which ultimately results in capacity degradation. Herein, the local stress and deformation evolution status of an SEI layer on an anode particle are investigated through a quantitative electrochemical-mechanical model. The impacts of structural uniformity, mechanical strength, and operating conditions on the stability of the SEI layer are investigated in detail. The simulation results demonstrate that when the silicon particle radius decreases from 800 ​nm to 600 and 400 ​nm, the failure time increases by 29% and 65%, respectively, of the original failure time; When the structural defect depth ratio is reduced from 0.6 to 0.4 and 0.2, the failure time increases by 72% and 132%, respectively; For the discharge rate, the condition at 0.1 C has 34% and 139% longer time to failure than that at 0.2 C and 0.3 C, respectively. This work provides insight into the rational design of stable SEI layers and sheds light on possible methods for constructing silicon-based lithium-ion batteries with longer cycling lives.

Conductive copper ion-reinforced sodium alginate aerogel based free-standing Si anode for Li-ion storage

Biomass materials with great advantages of wide accessibility, low cost and environmental benignity have favorable application prospects as Si anodes for lithium-ion batteries (LIBs). In order to alleviate the volume effect and improve the conductance of Si, we fabricated a conductive copper ion-reinforced sodium alginate (SA) aerogel based free-standing Si anode (Si@CNTs/Alg-Cu-II) containing silicon nanoparticles, sodium alginate aerogel, carbon nanotubes and Cu nanoparticles, via a simple, low-cost and sustainable process (under 1 × 10−1 Pa, 1 °C/min to 200 °C holding for 1 h). In the irregular lamellar porous aerogel, silicon particles with good dispersion are bound by macromolecular chains of SA via dynamic hydrogen bonds and subsequently restrained in the porous aerogel to release volume stress. The in situ generated Cu particles and well-dispersed carbon nanotubes (CNTs) construct the conductive network around Si particles to improve the electrical conductivity of the electrode. This unique structure delivers a capacity of 835.6 mAh/g after 100 cycles at 0.1 A/g based on the total mass of Si@CNTs/Alg-Cu-II composite (Si content of 25.62%). Moreover, it also shows outstanding stability under high current density (a capacity retention of 84.1% after 100 cycles at 0.5 A/g). The sustainable preparation method and excellent electrochemical performance of Si@CNTs/Alg-Cu-II provide a new strategy to develop high-performance free-standing Si-based anodes for LIBs.

Study on the Preparation of Silicon-Based Anode Materials with Porous Structure by Etching

Silicon has the advantages of high specific capacity (4200 mAh/g), low lithium potential and abundant reserves, and is considered to be one of the most suitable materials for replacing graphite negative electrode. However, the commercial silicon particle size is too large to be used directly as an electrode material, and the silicon material will undergo huge volume expansion during the lithium insertion process, resulting in the fragmentation of the active substance falling off from the fluid collector, resulting in a sharp decline in battery capacity. This defect seriously affects the commercial application of silicon-based anode materials. In this paper, a kind of silicon anode material with porous structure is designed for the defect of silicon anode material. The aluminum-silicon alloy prepared by atomization method presents a three-dimensional porous spherical structure after etching, and the abundant holes reserve space for the volume expansion during the process of lithium silicon embedding and improve the transmission rate of lithium ions. It was found that when the silicon content was 12%, the reversible specific capacity of the material was 1269 mAh/g at 4000 mA/g current density, and the capacity retention rate of 100 cycles relative to the fourth cycle was 59.5%. Compared with ball-ground silicon, the capacity retention rate is increased by 25.7%. Therefore, this paper provides a new idea for the design of porous silicon-based anode materials.

Boron-doped three-dimensional porous carbon framework/carbon shell encapsulated silicon composites for high-performance lithium-ion battery anodes

Deleterious volumetric expansion and poor electrical conductivity seriously hinder the application of Si-based anode materials in lithium-ion batteries (LIBs). Herein, boron-doped three-dimensional (3D) porous carbon framework/carbon shell encapsulated silicon (B-3DCF/Si@C) hybrid composites are successfully prepared by two coating and thermal treatment processes. The presence of 3D porous carbon skeleton and carbon shell effectively improves the mechanical properties of the B-3DCF/Si@C electrode during the cycling process, ensures the stability of the electrical contacts of the silicon particles and stabilizes the solid electrolyte interface (SEI) layer, thus enhancing the electronic conductivity and ion migration efficiency of the anode. The developed B-3DCF/Si@C anode has a high reversible capacity, excellent cycling stability and outstanding rate performance. A reversible capacity of 1288.5 mAh/g is maintained after 600 cycles at a current density of 400 mA g−1. The improved electrochemical performance is demonstrated in a full cell using a LiFePO4-based cathode. This study presents a novel approach that not only mitigates the large volume expansion effects in LIB anode materials, but also provides a reference model for the preparation of porous composites with various functionalities.

ATLAS ITk strip detector for the Phase-II Upgrade

The inner detector of the present ATLAS experiment has been designed and developed to function in the environment of the present Large Hadron Collider (LHC). At the ATLAS Phase-II Upgrade, the particle densities and radiation levels will exceed current levels by a factor of ten. The instantaneous luminosity is expected to reach unprecedented values, resulting in up to 200 proton-proton interactions in a typical bunch crossing. The new detectors must be faster and they need to be more highly segmented. The sensors used also need to be far more resistant to radiation, and they require much greater power delivery to the front-end systems. At the same time, they cannot introduce excess material which could undermine tracking performance. For those reasons, the inner tracker of the ATLAS detector was redesigned and will be rebuilt completely. The ATLAS Upgrade Inner Tracker (ITk) consists of several layers of silicon particle detectors. The innermost layers will be composed of silicon pixel sensors, and the outer layers will consist of silicon microstrip sensors. This contribution focuses on the strip region of the ITk. The central part of the strip tracker (barrel) will be composed of rectangular short (∼2.5 cm) and long (∼5 cm) strip sensors. The forward regions of the strip tracker (end-caps) consist of six disks per side, with trapezoidal shaped sensors of various lengths and strip pitches. After the completion of final design reviews in key areas, such as Sensors, Modules, Front-End electronics, and ASICs, a large scale prototyping program has been completed in all areas successfully. We present an overview of the Strip System and highlight the final design choices of sensors, module designs and ASICs. We will summarise results achieved during prototyping and the current status of pre-production and production on various detector components, with an emphasis on QA and QC procedures.

Oxidation of silicon particles suspended in a mullite matrix with dual-mode vacancy diffusion of oxygen

Mullite bond coats filled with silicon particles have recently been proposed for the next generation of environmental barrier coatings (EBC). The sacrificial oxidation of the silicon particles eliminates some of the environmental durability issues associated with traditional EBC designs. To investigate this novel design approach, a mathematical formulation and resulting numerical method have been developed for simulating the oxidation of silicon particles embedded in a mullite matrix. The focus is on the oxidation of the silicon in a dry oxygen environment where the oxidant is presumably oxygen. Oxygen transport from the exterior environment through the mullite is assumed to occur via two lattice defect diffusion mechanisms. As a result, the rate of oxygen transport is dictated by the self-diffusivity of the lattice defects. The numerical method is implemented using the COMSOL Multiphysics® Program. The method is applied to simulate the oxidation of silicon particles in a mullite pellet in recent oxidation experiments. Numerical results compare favorably with the oxidation behavior observed in the oxidation experiments. The numerical method is also used to investigate the effects of various features of the mullite/silicon particle system on the oxidation behavior.

Squeeze casting of 4032 aluminum alloy and the synergetic enhancement of strength and ductility via Al-Ti-Nb-B grain refiner

The 4032 aluminum alloy is a high-Si deformation aluminum alloy, that is commonly generated through forging due to the difficulties involved in its direct casting. In this work, the 4032 aluminum alloy is innovatively prepared via a squeeze casting process, and the Al-6Nb-1.5Ti-0.5B refining agent is incorporated to enhance its mechanical properties. A range of analytical techniques are subsequently employed to analyze the grain refinement mechanism of Al-6Nb-1.5Ti-0.5B under squeeze casting conditions. It was found that the microstructure of the aged 4032 aluminum alloy after refinement treatment was mainly composed of α-Al grains measuring <100 μm in size, in addition to a eutectic Si phase, that is accompanied by stacked dislocations and diffusely distributed Q′-Al5Cu2Mg8Si6 and θ′-Al2Cu phases. The yield strength of the alloy reached 340 MPa, its tensile strength was 404 MPa, and the elongation was 4.1 %. In the presence of the Al-6Nb-1.5Ti-0.5B refiner, the generation of nucleation cores (e.g., MAl3(M = Ti, Nb)) in the melt led to a significant reduction (∼50 %) in the α-Al grain size of the aged 4032 aluminum alloy (i.e., 95.1 ± 21.0 μm), compared with the standard alloy. After the T6 heat treatment of the refined 4032 aluminum alloy, the size of the precipitation phase was reduced by 36.8 %, and fine silicon particles with a spherical morphology and a more random distribution were observed. No obvious selective orientation was detected, and the fracture morphology improved significantly, thereby leading to a synergistic improvement in the strength and toughness of the alloy.

A Rapid, Scalable Laser-Scribing Process to Prepare Si/Graphene Composites for Lithium-Ion Batteries.

Silicon has gained significant attention as a lithium-ion battery anode material due to its high theoretical capacity compared to conventional graphite. Unfortunately, silicon anodes suffer from poor cycling performance caused by their extreme volume change during lithiation and de-lithiation. Compositing silicon particles with 2D carbon materials, such as graphene, can help mitigate this problem. However, an unaddressed challenge remains: a simple, inexpensive synthesis of Si/graphene composites. Here, a one-step laser-scribing method is proposed as a straightforward, rapid (≈3min), scalable, and less-energy-consuming (≈5W for a few minutes under air) process to prepare Si/laser-scribed graphene (LSG) composites. In this research, two types of Si particles, Si nanoparticles (SiNPs) and Si microparticles (SiMPs), are used. The rate performance is improved after laser scribing: SiNP/LSG retains 827.6mAhg-1 at 2.0AgSi+C -1, while SiNP/GO (before laser scribing) retains only 463.8mAhg-1. This can be attributed to the fast ion transport within the well-exfoliated 3D graphene network formed by laser scribing. The cyclability is also improved: SiNP/LSG retains 88.3% capacity after 100 cycles at 2.0AgSi+C -1, while SiNP/GO retains only 57.0%. The same trend is found for SiMPs: the SiMP/LSG shows better rate and cycling performance than SiMP/GO composites.

High voltage electrolytes for lithium-ion batteries with micro-sized silicon anodes

Micro-sized silicon anodes can significantly increase the energy density of lithium-ion batteries with low cost. However, the large silicon volume changes during cycling cause cracks for both organic-inorganic interphases and silicon particles. The liquid electrolytes further penetrate the cracked silicon particles and reform the interphases, resulting in huge electrode swelling and quick capacity decay. Here we resolve these challenges by designing a high-voltage electrolyte that forms silicon-phobic interphases with weak bonding to lithium-silicon alloys. The designed electrolyte enables micro-sized silicon anodes (5 µm, 4.1 mAh cm−2) to achieve a Coulombic efficiency of 99.8% and capacity of 2175 mAh g−1 for >250 cycles and enable 100 mAh LiNi0.8Co0.15Al0.05O2 pouch full cells to deliver a high capacity of 172 mAh g−1 for 120 cycles with Coulombic efficiency of >99.9%. The high-voltage electrolytes that are capable of forming silicon-phobic interphases pave new ways for the commercialization of lithium-ion batteries using micro-sized silicon anodes.

Interface Engineering Enables Wide-Temperature Li-Ion Storage in Commercial Silicon-Based Anodes.

Silicon-based materials have been considered potential anode materials for next-generation lithium-ion batteries based on their high theoretical capacity and low working voltage. However, side reactions at the Si/electrolyte interface bring annoying issues like low Coulombic efficiency, sluggish ionic transport, and inferior temperature compatibility. In this work, the surface Al2 O3 coating layer is proposed as an artificial solid electrolyte interphase (SEI), which can serve as a physical barrier against the invasion of byproducts like HF(Hydrogen Fluoride) from the decomposition of electrolyte, and acts as a fast Li-ion transport pathway. Besides, the intrinsically high mechanical strength can effectively inhibit the volume expansion of the silicon particles, thus promoting the cyclability. The as-assembled battery cell with the Al2 O3 -coated Si-C anode exhibits a high initial Coulombic efficiency of 80% at RT and a capacity retention ratio up to ≈81.9% after 100 cycles, which is much higher than that of the pristine Si-C anode (≈74.8%). Besides, the expansion rate can also be decreased from 103% to 50%. Moreover, the Al2 O3 -coated Si-C anode also extends the working temperature from room temperature to 0 °C-60 °C. Overall, this work provides an efficient strategy for regulating the interface reactions of Si-based anode and pushes forward the practical applications at real conditions.

Influence of Fe content on the microstructure and mechanical properties of Al-7Si-0.7Mg-2.8Fe alloy processed by laser powder bed fusion

Iron contamination is a major concern in aluminum alloys recycling. It is considered the main deleterious contamination due to its low solubility in the aluminum matrix leading to the formation of Fe-rich intermetallic phases with platelet-like morphology, which act as stress risers deteriorating the mechanical properties. This paper investigates the effect of Fe contamination in the microstructure and mechanical properties of Al–7Si-0.7Mg-2.8Fe alloy processed by Laser Powder Bed Fusion (LPBF). Microstructure characterization was carried out by Optical Microscopy (OM), X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM), and Transmission Electron Microscope (TEM). The mechanical characterization was performed by Vickers microhardness and tensile tests. The LPBF sample was analyzed in two directions, vertical and horizontal. The results show that the LPBF process provided a microstructural refinement and reduction of the aspect ratio of α-AlFeSi phase and silicon particles, leading to a strong improvement in mechanical properties when compared to the Fe-contaminated as-cast Al–7Si-0.7Mg-2.8Fe alloy.

Enhancing Li‐ion Battery Performance through the Integration of Si@TiO2 Core‐Shell Nanoparticles with Natural Graphite

AbstractIn this study, Si@TiO2 core‐shell nanoparticles are synthesized using the peptization technique, resulting in a thin and uniform TiO2 coating layer over silicon nanoparticles. This coating layer serves the purpose of controlling the structural degradation of the silicon nanoparticles. These core‐shell nanoparticles are then reinforced into the natural graphite with the potential to be used as a composite anode material (Graphite/Si@TiO2) for Li‐ion batteries. The developed composite material exhibits an initial specific capacity of ≈675 mAh/g at 0.5 A/g, and after 100 cycles it retains the capacity of 75 %. Compared with Graphite/Si composite anode, the developed composite anode material shows improved cyclic stability. The pre‐and post‐cycling morphological analysis of Graphite/Si and Graphite/Si@TiO2 composite anode reveals the degradation behavior. It is assumed that the TiO2 coating provides a protective shield for the silicon particles, preventing their interaction with the electrolyte and causing less material to deposit over the anode surface. Electrochemical Impedance Spectroscopy (EIS) analysis supports these findings, with the Graphite/Si composite anode exhibiting higher resistance than the Graphite/Si@TiO2 anode. In conclusion, the study demonstrates the potential of using Si@TiO2 core‐shell nanoparticles as a reinforcing agent for natural graphite to develop high‐performance composite anode material for Li‐ion batteries.

Improving the performance of lithium-ion batteries by micron-sized silicon particles coated with nano-ZnS anode materials

Micron-sized Si-based materials have attracted extensive attention for lithium-ion batteries due to their high theoretical capacity and low cost. However, its large volume expansion and low conductivity limit its further development. Here, a Si/ZnS anode material is prepared, in which ZnS nanoparticles are uniformly attached to the surface of micro-Si particles. The conversion reaction of ZnS generates metal Zn and Li2S, and the alloying reaction of Zn generates LixZn, the metal Zn and LixZn are used as conductive additives to improve the conductivity of the composites, while Li2S is used as an artificial solid electrolyte interfacial phase to promote the stability of the solid electrolyte interface of the composites, so that the prepared micron-sized Si-based anode exhibits excellent cycling stability. At a current density of 0.5 A g−1, the initial coulombic efficiency reaches 78.67 % and the discharge specific capacity is 1540.2 mAh g−1 after 200 cycles.

Silicon/Silicon Carbide/Graphite Composite Anode Material for Rechargeable Lithium-Ion Batteries by High-Temperature Vacuum Adsorption Method

Recently, the electrode materials for next-generation lithium-ion batteries (LIBs) draw widespread attention on storing reversibly the electrical energy. For this issue, the expanded graphite and silicon particles are chosen to generate silicon/silicon carbide/graphite composite anode material using a high-temperature vacuum adsorption method. The prepared composites are measured by X-ray diffraction, transmission electron microscopy, and Raman spectra, et al. The composites are cycled at a current density of 50 mA g-1, in order to observe their potential specific capacity. An initial charge capacity is 566.5 mAh g-1, and its initial Coulombic efficiency is 97.4 %. The reversible specific capacity keeps at 502 mAh g-1 after 80 cycles, displaying a capacity retention of 88.7%

A porous silicon composite with irregular silver nano-dendritic particles: a rapid optical sensor for trace detection of malachite green in freshwater fish.

This study focused on creating a SERS composite particle specifically designed for detecting malachite green. We synthesized silver nano-dendritic structures on p-type porous silicon using an external electric field, separating them from the silicon wafer. Ultrasonic crushing yielded irregular silver nanodendrite-modified porous silicon composite particles. Upon being tested in an aqueous solution of malachite green, these composite particles demonstrated significant surface-enhanced Raman scattering effects. Our findings highlight the exceptional performance of the SERS substrate composed of porous silicon and irregular silver nano-dendritic particles. It exhibited high sensitivity, specificity, consistent signal strength, and reliability in detecting trace amounts of malachite green in water. Under ideal conditions, the substrate could detect malachite green at concentrations as low as 10-8 M. Moreover, its swift response to trace amounts of malachite green in fish underscores its potential as an effective Raman detector.

Highly Tunable Dielectric Nano Antenna Consisting Chain of Silicon Particles by Dipole Emitter

Highly Tunable Dielectric Nano Antenna Consisting Chain of Silicon Particles by Dipole Emitter

Rapid, in situ synthesis of ultra-small silicon particles for boosted lithium storage capability through ultrafast Joule heating.

High-capacity anodes, especially silicon, suffer from huge volume fluctuations and electrode material pulverization during lithiation/delithiation. An accessible solution to this issue is to construct nano-silicon anodes with optimized particle size and a conductive matrix. In this work, we introduce a novel strategy for the in situ, rapid synthesis of ultra-small silicon nanoparticles uniformly embedded within carbonized nanosheets (us-Si/C) through swift high-temperature thermal radiative heating of sizable silicon nanoparticles (SiNPs). The us-Si/C anode shows ample capability to accommodate volume fluctuations during the lithiation/delithiation processes. The as-prepared anode exhibits a specific capacity of 920 mA h g-1 after 1000 cycles at a current density of 2 A g-1, indicating the advantages of the well-tailored structure. Additionally, the us-Si/C electrode can maintain an areal capacity of approximately 1.55 mA h cm-2 after 200 cycles at a high loading of 3.66 mg cm-2. Moreover, it presents practical applicability when assembled into LFP (lithium iron phosphate)//us-Si/C full cells. This preparation method presents great promise for achieving roll-to-roll manufacturing for practical applications due to its simplicity and efficiency.