Silicon Suboxide Research Articles

Enhanced mitochondrial fluorescence imaging through confinement fluorescence effect within a rigid silicon suboxide network

Fluorescence imaging technology has emerged as a powerful tool for studying intricate mitochondrial morphology within living cells. However, the need for fluorophores with stable fluorescence intensity and low phototoxicity poses significant challenges, particularly for long-term live-cell mitochondrial monitoring. To address this, we introduce the confinement fluorescence effect (CFE) into the design of fluorophores. This strategy involves confining small-molecule fluorophores within a silicon suboxide network structure of nanoparticles (CEF-NPs), which restricts molecular rotation, resulting in the suppression of non-radiative transition and the isolation of encapsulated fluorophores from surrounding quenching factors. CFE-NPs (SY2@SiOx) exhibit exceptional properties, such as high fluorescence intensity (80-fold) and reduced phototoxicity (0.15-fold). Furthermore, the TPP + -functionalized CFE-NPs (SY2@SiOxTPP) demonstrated efficacy in mitochondrial imaging and mitochondrial dynamics monitoring. Biochemistry assays indicated that SY2@SiOxTPP exhibits significantly lower phototoxicity to mitochondrial functions compared to both small-molecule fluorophore and commercial Mito Tracker. This approach allows for the long-term dynamic monitoring of mitochondrial morphological changes through fluorescence imaging, without impairing mitochondrial functionality.

Ab Initio Tomography Analysis of Lithium Incorporation and Diffusion in Multidomain Silicon Suboxide Anode Materials

Silicon is considered a promising anode material to supplant conventional graphite materials in lithium-ion batteries due to its higher theoretical energy-storage capacity compared to graphite. However, the widespread application of Si anodes has been hindered because the capacity of Si anodes decreases rapidly as the charge/discharge cycle proceeds. The controlled incorporation of oxygen into Si is often considered as a feasible approach for employing Si as an anode material in the form of silicon suboxide. Silicon suboxide exhibits a lower energy capacity compared to pure Si, but offers enhanced stability against volume expansion. Consequently, silicon suboxide materials have been commercialized by blending them with graphite. However, the blending ratio of silicon suboxide with graphite is limited to low levels due to its poor first-cycle efficiency, so-called initial Coulombic efficiency. In-depth understanding of the lithium interaction characteristics within multidomain silicon suboxide is indispensable for optimizing the electrochemical performance of silicon suboxide anode materials for lithium-ion batteries. In this study, we investigate the domain-dependent thermodynamic and kinetic properties of lithium atoms within systematically designed multidomain silicon suboxide models composed of Si, SiO2, and Si/SiO2 interface by performing a series of computational simulations combined with a unique tomography-like sampling scheme. We find that the Si/SiO2 interfacial region exhibits preferential thermodynamics and kinetics for lithiation and can serve as a critical lithium transport channel during charge-discharge cycles, while the SiO2 domain is likely to be excluded from lithiation due to its high resistance to lithium diffusion. Consequently, a significant fraction of lithium is expected to be trapped at the Si/SiO2 interface during the discharge process, which ultimately contributes to a low initial Coulombic efficiency. This theoretical understanding suggests that the formation of continuously connected lithium-transportable Si/SiO2 interfacial channels surrounding the Si domains, along with a well-structured shallow SiO2 framework through the use of appropriate synthesis methods, is essential for maximizing the electrochemical performance of silicon suboxide anode materials. Our theoretical approach offers new insights into the atomistic characteristics of silicon suboxide during lithiation/delithiation processes, ultimately enabling the identification of the origin of low ICE and strategies for addressing it.References(1) Chae, S.; Lim, H.-K.; Lee, S. Energy Landscapes for Lithium Incorporation and Diffusion in Multidomain Silicon Suboxide Anode Materials. ACS Applied Materials & Interfaces 2023, 15 (49), 57059-57069. DOI: 10.1021/acsami.3c12846. Figure 1

Osteointegration of functionalised high-performance oxide ceramics: imaging from micro-computed tomography

BackgroundThis study evaluated the osseointegration potential of functionalised high-performance oxide ceramics (HPOC) in isolation or coated with BMP-2 or RGD peptides in 36 New Zeeland female rabbits using micro-computed tomography (micro CT). The primary outcomes of interest were to assess the amount of ossification evaluating the improvement in the bone volume/ total volume (BV/TV) ratio and trabecular thickness at 6 and 12 weeks. The second outcome of interest was to investigate possible differences in osteointegration between the functionalised silanised HPOC in isolation or coated with Bone Morphogenetic Protein 2 (BMP-2) or RGD peptides.Methods36 adult female New Zealand white rabbits with a minimum weight of three kg were used. One-third of HPOCs were functionalised with silicon suboxide (SiOx), a third with BMP-2 (sHPOC-BMP2), and another third with RGD (sHPOC-RGD). All samples were scanned with a high-resolution micro CT (U-CTHR, MILabs B.V., Houten, The Netherlands) with a reconstructed voxel resolution of 10 µm. MicroCT scans were reconstructed in three planes and processed using Imalytics Preclinical version 2.1 (Gremse-IT GmbH, Aachen, Germany) software. The total volume (TV), bone volume (BV) and ratio BV/TV were calculated within the coating area.ResultsBV/TV increased significantly from 6 to 12 weeks in all HPOCs: silanised (P = 0.01), BMP-2 (P < 0.0001), and RGD (P < 0.0001) groups. At 12 weeks, the BMP-2 groups demonstrated greater ossification in the RGD (P < 0.0001) and silanised (P = 0.008) groups. Trabecular thickness increased significantly from 6 to 12 weeks (P < 0.0001). At 12 weeks, BMP-2 promoted greater trabecular thickness compared to the silanised group (P = 0.07), although no difference was found with the RGD (P = 0.1) group.ConclusionSinalised HPOC in isolation or functionalised with BMP-2 or RGD promotes in vivo osteointegration. The sinalised HOPC functionalised with BMP-2 demonstrated the greatest osseointegration.

Mechanistic insight into the impact of dry-state prelithiated SiOx thin-film anode toward extremely fast-charging and long-term stability

Silicon suboxides (SiOx) have achieved partial success in commercialization as high-capacity anode materials to replace graphite because of optimal electrochemical properties over silicon. Unfortunately, the further development has been sluggish, jeopardizing the urgent need of green energy. The daunting challenges to tackle include low initial coulombic efficiency (ICE) and low charging rate due to poor electron and ionic conductivity. In the context of thin film microbattery, we propose to precisely control the chemical states of SiOx films through varying sputtering power followed by dry-state pre-lithiation through Li-metal thermal evaporation, superior to the current pre-lithiation approaches for SiOx thin-film anodes. We addressed the leading roles of the surface chemical states of the as-deposited SiOx in the formation of the high ionic conductive Li4SiO4 phase as the pre-solid electrolyte interphase during the proposed dry-state prelithiation process. Ultimately, the prelithiated SiOx successfully mitigated the most confronted issues as low ICE and C-rate limitation, achieving an unprecedented rate performance of 72.8 % at 20 C, and ultra-long-cycle retention of 54.2 % over 5000 cycles at 10 C. These results strongly prove that appropriate pre-lithiation provides tremendous advantages to SiOx thin film anode not only in prolonging electrode stability but also promoting a significant fast-cycling.

Investigation of physical and electrical properties of a suboxide layer at Si/Si-hexafluoride interface

The silicon suboxide SiOx (x < 2.0) offers promising industrial application possibilities ranging from electrodes in lithium-ion batteries, which are used widely in electrical vehicles and portable devices to sensing applications. Therefore, a low cost, environmental friendly and high performance silicon oxide materials are required for an appropriate operation of any electronic gadget. In this work, we report on the physical and electrical properties of a suboxide layer of up to 1 μm, which was grown on silicon during the formation of a dielectric layer, namely the ammonium silicon hexafluoride. It is a stable oxide exhibiting light emission from 400 to 1700 nm offering scalable and cost-effective large area processing capability. The measurement results reveal interesting properties, which are required to be understood clearly before proceeding with any suitable application. The results have been analyzed using state-of-the-art physical and electrical characterization techniques such as ellipsometry, AFM, SEM, FTIR, photoluminescence lifetime and resistive switching measurements to determine structural, optical and electrical properties. At 300 K the carrier lifetime measurements reveal the lifetime values ranging from about few tens of picosecond up to 4500 picoseconds. Scanning probe analysis indicate a surface roughness of about 30 Å. Resistive memory forming was observed also in these layers at relatively low power thresholds. We provide a comprehensive description of the physical and electrical properties in order to clarify the origin of the observed features. The wavelength dependent real ε1(ω)\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\\varepsilon }_{1}(\\omega )$$\\end{document} and the imaginary ε2ω\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\\varepsilon }_{2}\\left(\\omega \\right)$$\\end{document} dielectric functions provided useful insights on optical properties. A lookout is given for the possible applications of this special SiOx dielectric oxide layer.

Dual-Carbon Phase-Encapsulated Prelithiated SiOx Microrod Anode for Lithium-Ion Batteries.

Among silicon-based anode family for Li-ion battery technology, SiOx, a nonstoichiometric silicon suboxide holds the potential for significant near-term commercial impact. In this context, this study mainly focuses on demonstrating an innovative SiOx@C anode design that adopts a pre-lithiation strategy based on in situ pyrolysis of Li-salt of silsesquioxane trisilanolate without the need for lithium metal or active lithium compounds and creates dual carbon encapsulation of SiOC nanodomains by simply one-step thermal treatment. This ingenious design ensures the pre-lithiation process and pre-lithiation material with high-environmental stability. Moreover, phenyl-rich organosiloxane clusters and polyacrylonitrile polymers are expected to serve as internal and external carbon source, respectively. The formation of an interpenetrating and continuous carbon matrix network would not only synergistically offer an improved electrochemical accessibility of active sites but also alleviate the volume expansion effect during cycling. As a result, this new type of anode delivered a high reversible capacity, remarkable cycle stability as well as excellent high-rate capability. In particular, the L2-SiOx@C material has a high initial coulomb efficiencof 80.4% and, after 500 cycles, a capacity retention as high as 97.5% at 0.5 A g-1 with a reversible specific capacity of 654.5mA h g-1.

Making Room for Silicon: Including SiOx in a Graphite-Based Anode Formulation and Harmonization in 1 Ah Cells

Transitioning to more ambitious electrode formulations facilitates developing high-energy density cells, potentially fulfilling the demands of electric car manufacturers. In this context, the partial replacement of the prevailing anode active material in lithium-ion cells, graphite, with silicon-based materials enhances its capacity. Nevertheless, this requires adapting the rest of the components and harmonizing the electrode integration in the cell to enhance the performance of the resulting high-capacity anodes. Herein, starting from a replacement in the standard graphite anode recipe with 22% silicon suboxide at laboratory scale, the weight fraction of the electrochemically inactive materials was optimized to 2% carbon black/1% dispersant/3% binder combination before deriving an advantage from including single-wall carbon nanotubes in the formulation. In the second part, the recipe was upscaled to a semi-industrial electrode coating and cell assembly line. Then, 1 Ah lithium-ion pouch cells were filled and tested with different commercial electrolytes, aiming at studying the dependency of the Si-based electrodes on the additives included in the composition. Among all the electrolytes employed, the EL2 excelled in terms of capacity retention, obtaining a 48% increase in the number of cycles compared to the baseline electrolyte formulation above the threshold capacity retention value (80% state of health).

Carbon nanotubes anchored SiOx composite anode for high cyclic stability lithium-ion batteries

Silicon suboxide (SiOx, 0 < x < 2) is one of the most promising anode materials because of its high lithium-ion storage capacity. However, the poor intrinsic conductivity and large volume change during cycling limits its practical application as lithium-ion battery anode materials. Herein, we propose a novel strategy to introduce carbon nanotubes (CNTs) on the SiOx particles, forming a conductive network and relieving the volume expansion effect, which possess improved reversible capacity and robust structure for long cycling stability. The SiOx/CNT composite anode delivers reversible capacity of 1533.8 mAh g−1 at the first cycle and maintains 599.6 mAh g−1 after 500 cycles with a high coulombic efficiency of 99.7 %. In this paper, SiOx composite anchored by CNTs was prepared, which is a simple and effective strategy to improve the conductivity of SiOx, relieve the volume effect and further promote its electrochemical performance benefit from the high conductivity and structural stability of CNTs. This research provides a significant reference for constructing the delicate structure of SiOx-based composites to enhance cyclic performance.

Fabrication of fluidic submicron-channels by pulsed laser-induced buckling of SiOx films on fused silica

Recently, considerable attention has been drawn to the field of micro/nanofluidic channels. However, current methods for fabricating micro/nanochannels are complex, costly, and time-intensive. In the present work, we successfully fabricated transparent submicron-channels on fused silica substrates (SiO2) using a straightforward laser process. To achieve this, a single-pulse excimer laser irradiation in a rear side configuration was employed to treat a thin film of UV-absorbing silicon suboxide (SiOx) through the transparent SiO2 substrate. A polydimethylsiloxane (PDMS) superstrate (coating layer) was applied over the SiOx film before laser exposure, serving as a confinement for controlled structure formation induced by the laser. Under optimal laser fluence, the thin SiOx film buckled, leading to the formation of channels with a width ranging from 10 to 20 µm and a height of 800 to 1200 nm, exhibiting a bell-like cross-sections following the so-called Euler buckling mode. Wider channels displayed morphologies resembling varicose or telephone cord modes. Subsequent high-temperature annealing led to the oxidation of SiOx, resulting transparent SiO2 channels on the fused silica substrate. The manufactured nanochannels exhibited promising potential for effectively transporting fluids of diverse viscosities. Various fluids were conveyed through these nanochannels via capillary action and in accordance with the Lucas-Washburn equation.

MOF-derived cobalt nanoparticles in silicon suboxide-based anodes for enhanced lithium storage

The ultra-high theoretical capacity of silicon-based (Si) materials makes them promising anode materials for high energy density lithium-ion batteries. Unfortunately, the dramatic volume change (∼300%) and low electrical conductivity of silicon have severely hindered the commercial use of silicon anodes. Silicon suboxide (SiOx) is one of the ideal candidates for high energy density batteries due to its reduced swelling and lower cost as compared to silicon. However, it remains a huge challenge to address the low conductivity, low (initial) coulombic efficiency and apparent volume effects of SiOx. In this paper, SiOx/Co@C composite anode materials loaded with metal Co nanoparticles were uniformly and efficiently prepared by using 3-aminopropyl triethoxysilane (APTES) as silicon source and Co-MOF as Co source via molecular self-assembly strategy. The experimental results and density functional theory (DFT) calculation showed that the catalytic action of embedded Co nanoparticles had activated the silico-oxygen bond of SiOx and the irreversible product Li2O, thereby improving the initial coulombic efficiency (ICE) and enhancing the reversible capacity. At the same time, the metal Co with mechanical rigidity and electrical conductivity alleviated the volume fluctuation during alloying and improved the charge transfer capacity and ion transport rate of the composite. When compared with SiOx@C anodes, SiOx/Co@C-600 composites showed higher initial CE, superior cyclic stability and good rate performance. In particular, the successful matching of the anode with the lithium iron phosphate (LFP) cathode in full cell systems validated the possibility of its practical application. This work provides important insights into the application of Si-based materials in lithium-ion battery electrode materials and the development of high energy density batteries.

Co-synthesis and Electrochemical Investigation of the Nitrogen-Doped Carbon Layer with Metallic Nano Beads on the SiOx Anode for Lithium Secondary Batteries.

The high theoretical capacity (∼2000 mAh g-1) of silicon suboxide (SiOx, with 1 < x < 2) can solve the energy density issue of the graphite anode in Li-ion batteries. In addition, it has an advantage in terms of volume expansion or side reactions compared to pure Si or Li metals, which are considered as next-generation anode materials. However, the loading content of SiOx is limited in commercial anodes because of its low cycle stability and initial coulombic efficiency. In this study, a nitrogen-doped carbon layer with Cu beads (N-C/Cu) derived from copper phthalocyanine (CuPc) is applied to a SiOx electrode to improve its electrochemical performance. The SiOx electrode is simultaneously coated with a Cu- and N-doped carbon layer using CuPc. N-C/Cu synergistically enhances the electric conductivity of the electrode, thus improving its electrochemical performance. The SiOx/N-C/Cu composite has better cyclability and higher capacity (1095.5 mAh g-1) than the uncoated electrode, even after 200 cycles in the 0.5 C condition. In full-cell cycling with NCM811 cathodes, the SiOx (60 wt % of SiOx, with a n/p ratio of 1.1) and graphite-mixed (7.8 wt % of SiOx, with a n/p ratio of 1.1) anodes also show improved electrochemical performances in the same conditions.

A Scalable and Effective Strategy for Boosting the Initial Coulombic Efficiency of Silicon Suboxide Anode

Silicon suboxide (SiO x ) is one of the most attractive candidates for anode materials for high-energy-density lithium-ion batteries due to its high specific capacity and its relatively lower volume expansion than that of Si. However, its low initial Coulombic efficiency (ICE) seriously affects its practical applications. In this work, we demonstrate a scalable and effective strategy to enable a high ICE of the SiO x electrode through a MnO-assisted disproportionation reaction. The obtained Mn 2 SiO 4 –Si–SiO x @C (MSS@C) material shows a reduced lithium irreversible consumption in the first cycle. The Mn 2 SiO 4 phase can store lithium through a conversion reaction with a smaller volume change (33%) than SiO x , which helps to maintain the structural stability of MSS@C during cycling. Meanwhile, the metallic Mn nanoparticles generated from Mn 2 SiO 4 during the lithiation process facilitate electron conduction, thus improving the electrode reaction kinetics. Owing to the synergetic effects, the MSS@C material exhibits a higher ICE (79.51%) compared to 60.91% of pure SiO x , and a superior cyclic performance (832 mAh g −1 at 0.5 A g −1 after 350 cycles with a capacity retention of 90.4%). This work offers a new approach to increase the ICE while improving the electrode reaction kinetics and cycling stability of SiO x -based materials.

Confining micron silicon suboxide (μ-SiOx) into an N-doped carbon matrix modified by Sn nanoparticles as a stabilized anode material for fast charging lithium-ion batteries

Utilizing Sn-modified N-doped carbon networks to encapsulate SiOx to maintain its stability and facilitate lithium-ion and electron migration during charge/discharge.

Energy Landscapes for Lithium Incorporation and Diffusion in Multidomain Silicon Suboxide Anode Materials.

In-depth understanding of the lithium interaction characteristics within multidomain silicon suboxide is indispensable for optimizing the electrochemical performance of silicon suboxide anode materials for lithium-ion batteries. In this study, we investigate the domain-dependent thermodynamic and kinetic properties of lithium atoms within systematically designed multidomain silicon suboxide models composed of Si, SiO2, and Si/SiO2 interface by performing a series of computational simulations combined with a unique tomography-like sampling scheme. We find that the Si/SiO2 interfacial region exhibits preferential thermodynamics and kinetics for lithiation and can serve as a critical lithium transport channel during charge-discharge cycles, while the SiO2 domain is likely to be excluded from lithiation due to its high resistance to lithium diffusion. Consequently, a significant fraction of lithium is expected to be trapped at the Si/SiO2 interface during the discharge process, which ultimately contributes to a low initial Coulombic efficiency. This theoretical understanding suggests that the formation of continuously connected lithium-transportable Si/SiO2 interfacial channels surrounding the Si domains, along with a well-structured shallow SiO2 framework through the use of appropriate synthesis methods, is essential for maximizing the electrochemical performance of silicon suboxide anode materials.

Hybrid crosslinking for in-situ encapsulation of three-dimensional porous SiOx@rGO as high-performance anodes in lithium-ion batteries

Silicon suboxide (SiOx) anodes have garnered significant attention from both academia and industry due to their superior theoretical capacity compared to graphite, as well as their improved capacity retention in comparison to pure silicon. Nevertheless, SiOx electrodes still confront the challenge of substantial volume expansion (>160 %) during the alloying process, resulting in electrode structural damage or even fragmentation and severely impacting cycling performance. Here, a three-dimensional (3D) conductive network was constructed by ethylenediamine (EDA) cross-linking reduced graphene oxide (rGO), which was encapsulated on the surface of SiOx spheres generated in situ via a magnesium thermal reduction reaction. Accordingly, the SiOx@rGO-EDA anode was prepared successfully with high reversible capacity (892 mAh g−1 after 100 cycles at 1 A g−1) and fascinating rate performance (447 mAh g−1 at 4 A g−1). In full cell, the SiOx@rGO-EDA anode also exhibits outstanding cycling stability (154 mAh g−1 after 100 cycles at 0.1C) and rate capability. The scanning electron microscopy (SEM) images captured from a top-view perspective indicate that the surface of SiOx@rGO-EDA electrode is smooth and dense without any noticeable cracks, and it maintains its structural integrity throughout the cycling process. The cross-sectional thickness of the electrode remains essentially the same. These results illustrate the superior structural stability of the EDA cross-linked graphene conductive network cladding structure, enabling it to adapt to dynamic changes and ensure efficient transport of lithium ions and electrons. The facile and versatile synthesis method of SiOx@rGO-EDA structures by incorporating cross-linking agents provides inspiration for the design of next-generation high-performance anodes.

Picosecond versus femtosecond-laser ablation of silicon in atmosphere

Laser ablation (LA) using nanosecond (ns) or femtosecond (fs) pulse widths is well-established for the volatilization of a liquid or solid for applications ranging from micromachining to sampling for compositional analysis. Far less work has examined laser ablation in the intermediate picosecond regime (ps-LA), which corresponds to the approximate timescale for the transfer of energy from laser-excited electrons to the lattice. 213 and 355 nm ps-LA of silicon (Si) with Gaussian beam profiles is compared here to 800 nm fs-LA with both Gaussian and flat-top beam profiles, all performed at or above the ablation threshold with 20 000–67 000 laser pulses. The morphology and composition of the ablation spots are examined using scanning electron microscopy and energy dispersive x-ray spectroscopy (EDS), respectively. 213 nm ps-LA yields more visible nanostructures compared to those ablated by 355 nm ps-LA, but both form central craters with surrounding nanostructures due to resolidified material. The flat-top fs beam creates protruding nanostructures isolated near the rim of the crater and an inside-out umbrella-like structure at the center. The Gaussian fs-LA region displays a relatively smooth conical crater, albeit with some nanostructure at the rim of the crater. EDS finds that these nanostructures are at least partly composed of silicon oxide or suboxides. The invisibility of these nanostructures to optical profilometry is consistent with black-silicon. The ablation crater results from optical profilometry for 213 nm ps-LA are close to those for 800 nm flat-top fs-LA, and both are consistent with cylindrical craters.

Electrolyte design for lithium-ion batteries with a cobalt-free cathode and silicon oxide anode

Lithium-ion batteries (LIBs) to power electric vehicles play an increasingly important role in the transition to a carbon neutral transportation system. However, at present the chemistry of LIBs requires, among other elements, cobalt (Co), which will probably become scarce over time in addition to posing supply chain risks related to its single source, human rights and mining practices. To address this problem, we construct a LIB pairing a Co-free cathode with a silicon suboxide (SiOx) anode that possesses a high cut-off voltage of 4.9 V and sustains unprecedented 1,000 cycles. Underlying this favourable electrode combination is a rational electrolyte design based on 3.4 M LiFSI/FEMC featuring a shifted potential, which serves to aid formation of robust passivation layers on the anode and promote electrolyte stability against both reductive and oxidative degradations. Our electrolyte formulation offers a pathway towards both sustainable and high-performing LIBs, while the concept could be applied to other electrochemical energy technologies.

Effect of Plasma Oxygen Content on the Size and Content of Silicon Nanoclusters in Amorphous SiOx Films Obtained with Plasma-Enhanced Chemical Vapor Deposition

The influence of Ar + SiH4 + O2 plasma formulation on the phase composition and optical properties of amorphous SiOx films with silicon nanoclusters obtained using PECVD with DC discharge modulation was studied. Using a unique technique of ultrasoft X-ray emission spectroscopy, it was found that at a 0.15 mol.% plasma oxygen content, amorphous silicon a-Si films are formed. At a high oxygen content (≥21.5 mol.%), nanocomposite films based on SiOx silicon suboxide containing silicon nanoclusters ncl-Si are formed. It was found that the suboxide matrix consists of a mixture of SiO1.3 and SiO2 phases, and the average oxidation state x in the SiOx suboxide matrix is ~1.5. An increase in the concentration of O2 in the reactor atmosphere from 21.5 to 23 mol.% leads to a decrease in ncl-Si content from 40 to 15% and an increase in the average oxidation state x of SiOx from 1.5 to 1.9. In this case, the suboxide matrix consists of two phases of silicon dioxide SiO2 and non-stoichiometric silicon oxide SiO1.7. Thus, according to the experimental data obtained using USXES, the phase composition of these films in pure form differs in their representation in both random coupling and random mixture models. A decrease in the ncl-Si content of SiOx films is accompanied by a decrease in their sizes from ~3 to ~2 nm and a shift in the photoluminescence band from 1.9 eV to 2.3 eV, respectively.

Recent advances of SiO x -based anodes for sustainable lithium-ion batteries

The world is facing an ever-growing global energy crisis with unprecedented depth and complexity. The sustainable development of high energy density lithium-ion batteries for electric vehicles and portable electric devices has become a feasible way to deal with this problem. Silicon suboxides (SiO_<i>x</i>) have been deemed as one of the most promising anode materials because of their ultrahigh theoretical lithium storage capacity, proper working potential, natural abundance, and environmental friendliness. However, the mass utilization of SiO_<i>x</i>-based anodes is severely obstructed by their low electrical conductivity and inevitable volume expansion. While lithium silicate and lithium oxide formed in the first lithiation process act as buffer layers to some extent, it is urgent to address the accompanying low initial Coulombic efficiency and unsatisfactory cycling stability. In this review, we summarized recent advances in the synthesis methods of SiO_<i>x</i>-based materials. Besides, the benefits and shortcomings of the various methods are briefly concluded. Then, we discussed the effective combination of SiO_<i>x</i> with carbon materials and designs of porous structure, which could considerably enhance the electrochemical performance in detail. Furthermore, progresses on the modified strategies, advanced characteristics and industrial applications for SiO_<i>x</i>-based anodes are also mentioned. Finally, the remaining challenges encountered and future perspectives on SiO_<i>x</i>-based anodes are highlighted.

Surface Design Engineering of LiTaO3 Coating on Li-Excess Li2NiO2 Cathode Additive for Lithium-Ion Batteries

The latest research has mainly focused on enhancement in the energy density of lithium-ion batteries (LIBs) to satisfy the rigorous industrial demands. As the most common approach for improving the energy density of LIBs, the utilization of high capacity anode materials, such as silicon suboxide (SiOx), has been highlighted, instead of graphite. SiOx anodes are known to have a high specific capacity and low operating voltage (< 0.5 V vs. Li/Li+). However, the severe initial capacity loss induced by the formation of solid electrolyte interphase (SEI) limits their commercial use in LIBs. To compensate for the initial loss of available Li+, the application of Li-excess cathode additives has been considered as the most practical strategy for supplying surplus Li+ during the initial charge process. In this respect, Li2NiO2 is a suitable cathode additive because it offers a high initial charge capacity (≥ 320 mAh g-1) and a compatible operating voltage with commercial cathode materials. Surface protection of Li2NiO2 is still required, however, due to its vulnerability to moisture (H2O) and carbon dioxide (CO2) in the ambient atmosphere. Moreover, Li2NiO2 becomes more structurally unstable during cycle due to oxygen (O2) gas evolution, leading to the formation of microcracks. To overcome these obstacles, we suggest a functional LiTaO3 coating layer onto the surface of Li2NiO2 for structural stabilization. In practice, the LiTaO3 coating layer can effectively suppress the production of impurities (i.e., LiOH and Li2CO3) at the surface of Li2NiO2 after air exposure. Furthermore, the gas evolution and microcracks can be minimized by enhancing the structural stability of Li2NiO2 during cycling. These synergetic effects of the LiTaO3 coating layer can provide clear insights for the development of Li-excess cathode additives for achieving advanced LIBs.