Silicon Anodes Research Articles

Double Carbon-Species Coated Porous Silicon Anode Induced by Interfacial Energy Reduction for Lithium-Ion Batteries.

The rapid development of electric vehicles necessitates high-energy density Li-ion batteries for extended range. Silicon is a promising alternative to graphite anodes due to its high capacity; however, its substantial volume expansion during cycling leads to continuous growth of the solid electrolyte interphase and significant capacity fading. This study addresses these issues by designing a porous Si structure combined with a double carbon-species coating layer, induced by low interfacial energy in a scalable process. Carbon and graphene are located on Si surfaces, forming a close interface that maintains electrical contact, suppresses lithium consumption, and enhances charge transfer properties. The composite anode with a double carbon-species coating on Si demonstrates rapid stabilization with increasing coulombic efficiency, achieving a specific capacity of 1,814 mAh g-1 at 0.2 C and a high-rate capability of 1,356 mAh g-1 at 10C. Additionally, in a full-cell configuration with LiFePO4, it recorded a specific capacity of 161 mAh g-1 at 0.2 C. These results show the potential of porous Si with a carbon-graphene coating for stable, high-capacity operation in Li-ion batteries, offering new insights into high-performance electrochemical systems. Moreover, the double carbon-species coating derived from a scalable surface chemistry-based process presents a realistic alternative for industrial applications.

Progress in the application of silicon-based materials in lithium-ion batteries anodes

From the battery that powers the remote control to the battery that powers electric cars, lithium-ion batteries (LIBs) are a crucial component of contemporary energy storage. The large theoretical capacity of silicon anodes provides significant benefits inside LIBs. However, the main issue with the conventional silicon bulk anode is its considerable volume expansion, which forms an unstable Solid Electrolyte Interface (SEI) layer during the charge and discharge process and severely reduces battery performance and lifespan. Therefore, to solve these issues, researchers have explored multiple improved silicon anodes, three of which are mentioned in this essay. Firstly, the researchers delve into the usage of nanotechnology. When manipulating silicon particles at the nano-scale, the nano-silicon can mitigate the volume expansion, improving the reaction kinetics. Then, a composite of carbon and silicon is proposed, combining silicon's high capacitance and carbon's high conductivity. After that is the silicon-metal composite, which utilizes metals' mechanical strength and conductivity to stabilize Si anodes further and improve thermal stability. Overall, the significance of this study lies in the exploration of the application of silicon anodes in LIBs, highlighting the potential of these composite materials and advanced technology, which may help guide the future exploration of better silicon anodes.

Innovations in Energy Through Nanomaterials Enhancing Solid-State Battery Safety and Efficacy

This paper explores the potential of Si-based nanomaterials to enhance the performance of lithium-ion batteries (LIBs), particularly for electric vehicles (EVs). Traditional graphite anodes limit the energy density and range of EVs, increasing the need to search for alternative materials like silicon, which offers a much higher theoretical specific capacity. However, silicon’s application has been challenged by significant volume changes during cycling, leading to mechanical stress and failure. The use of nanotechnology, especially silicon nanomaterials, offers promising solutions to these challenges. Silicon nanostructures, such as nanowires, exhibit enhanced mechanical properties, allowing them to withstand volumetric changes and maintain high capacity during cycling. This review delves into the chemo-physical properties of silicon, the challenges posed by silicon anodes (SAs), and the recent advancements in silicon nanomaterials. Additionally, it also discusses different approaches to enhancing the performance of Si-based anodes, as well as the difficulties that exist now and the directions that future research in this exciting area is headed.

High‐Performance Yolk‐Shell Structured Silicon‐Carbon Composite Anode Preparation via One‐Step Gas‐Phase Deposition and Etching Technique

AbstractFor producing high‐capacity silicon (Si) anodes, a combined gas‐phase deposition and etching technique is developed to construct yolk‐shell structured silicon‐carbon composites. As a novel etching agent in battery field, NF3 is applied to selectively etch Si to tailor the architecture. Si particles as self‐sacrificed precursor have no need to build artificial or complex templates in advance, thereby greatly simplifying fabrication process and showcasing practicality. As a result, yolk‐shell structured silicon‐carbon composites are successfully fabricated in a single step. Sufficient buffer space between Si and carbon layer accommodates the significant expansion of Si during lithiation, preventing fracture of the carbon layer, which greatly improves service life of Si‐based anodes. Moreover, the refined particle size of Si and abundant pores in inner Si cores enhance the lithiation and de‐lithiation kinetic. Even with a high Si loading of 3.9 mg cm−2, the produced anode exhibits a superior areal capacity of 16.3 mAh cm−2 at 0.2 mA cm−2. Furthermore, at a high current density of 4 A g−1, it demonstrates an excellent capacity of 1114 mAh g−1 after 1000 cycles with a capacity retention of 96.3%. Additionally, with pre‐lithiation, it is successfully paired with an iron trifluoride cathode to construct high‐energy lithium‐ion batteries.

Rational design of alginate-derived network binder for high-performance silicon-based anodes in Li-ion batteries

This study developed a novel alginate-derived network binder, SAH, to enhance the performance and stability of silicon-based anodes in lithium-ion batteries. Integrating acrylic acid and 2-hydroxyethyl acrylate with sodium alginate through a one-pot polymerization and in-situ cross-linking method, SAH effectively addresses the volumetric expansion challenges associated with silicon anodes. This innovative binder maintains the structural integrity of the silicon anode through its rigid acrylic acid component, while the flexible acrylic-2-hydroxyethyl ester serves as a dynamic buffer to enhance flexibility. Sodium alginate contributes its intrinsic beneficial properties and imparts a robust three-dimensional network structure through effective coupling, allowing the binder to accommodate silicon volume changes during battery operation. Consequently, lithium-ion batteries incorporating this binder exhibited improved stability and extended cycle life, achieving an impressive capacity retention rate of 87.3 % after 100 cycles at 0.5C. This study highlights the potential of biopolymeric materials in enhancing the functionality of silicon-based anodes, contributing to the ongoing development of high-performance energy storage technologies.

Rectifying solid electrolyte interphase structure for stable multi-dimensional silicon anodes

Rectifying solid electrolyte interphase structure for stable multi-dimensional silicon anodes

In situ catalyzed growth of carbon nanotube with asphalt cladding as a bicarbon synergistic framework of silicon anodes for lithium-ion batteries.

Silicon, as the most promising advanced anode material for lithium-ion batteries, faces challenges in large-scale industrial production due to the significant volume expansion effect. In this investigation, Si/CNTs/C composite materials were effectively produced through high-temperature carbonization utilizing asphalt, silicon, hexahydrate ferric chloride, and melamine as primary elements. The distinctive dual-carbon framework of asphalt-derived carbon and carbon nanotubes alleviates the volume expansion of silicon, thereby stabilizing the composite material's structure. Testing the electrochemical performance reveals that the Si/CNTs/C composite material exhibits a reversible specific capacity of 1187 mAh g-1 with a capacity retention rate of 92.6% after 150 cycles at a current density of 0.2 A g-1. Even after 500 cycles at a current density of 1 A g-1, it sustains a specific capacity of 879.4 mAh g-1 with a capacity retention rate of 87.9%, showcasing outstanding electrochemical performance.

Synthesis Methods of Si/C Composite Materials for Lithium-Ion Batteries

Silicon anodes present a high theoretical capacity of 4200 mAh/g, positioning them as strong contenders for improving the performance of lithium-ion batteries. Despite their potential, the practical application of Si anodes is constrained by their significant volumetric expansion (up to 400%) during lithiation/delithiation, which leads to mechanical degradation and loss of electrical contact. This issue contributes to poor cycling stability and hinders their commercial viability, and various silicon–carbon composite fabrication methods have been explored to mitigate these challenges. This review covers key techniques, including ball milling, spray drying, pyrolysis, chemical vapor deposition (CVD), and mechanofusion. Each method has unique benefits; ball milling and spray drying are effective for creating homogeneous composites, whereas pyrolysis and CVD offer high-quality coatings that enhance the mechanical stability of silicon anodes. Mechanofusion has been highlighted for its ability to integrate silicon with carbon materials, showing the potential for further optimization. In light of these advancements, future research should focus on refining these techniques to enhance the stability and performance of Si-based anodes. The optimization of the compounding process has the potential to enhance the performance of silicon anodes by addressing the significant volume change and low conductivity, while simultaneously addressing cost-related concerns.

Performance Degradation Mechanism of the Si@N, S-Doped Carbon Anode in Sulfide-Based All-Solid-State Batteries.

Silicon (Si) anode is a promising anode material for all-solid-state lithium batteries with ultra-high theoretical specific capacity and low lithium dendrite risk. However, the inevitable vast volume expansion of Si anode during charge/discharge is recognized as a major limitation preventing its commercial application. Herein, an N, S self-doped amorphous carbon layer coated on porous micron-sized Si (p-mSi@C) is designed to construct an electron/ion conducting network while ensuring structural and interfacial stability. Uneven distribution of von mises stresses during p-mSi lithiation leads to irregular volume expansion and even fragmentation. Meanwhile, the growth of by-products at the interface between p-mSi and electrolyte contact leads to a rapid capacity decay. Compared to p-mSi anode, p-mSi@C reduces the risk of fragmentation thanks to the stress-absorbing effect of amorphous carbon, delivering excellent electrochemical performance (2679.65 mAh g-1 at 0.2 mA cm-2 with initial coulombic efficiency of 84%). More importantly, the chemical failure mechanisms of p-mSi and p-mSi@C composite anodes are revealed through structural characterization, chemical analysis, and simulation, which provides the necessary theoretical guidance for practicalization.

Earth-abundant, low-cost raw micro-silicon enabled by mechanically strengthened binder for high-capacity and long-life battery electrode

Nano-structured silicon materials with high capacity, are currently being gradually commercialized and composited with graphite in high-energy batteries, although their fabrication cost is rather high. However, the low-cost micro-silicon materials are always criticized and discarded in batteries due to the severe particle-to-electrode crack and huge volume change. Herein, inspired by the human ligament, a cross-linked binder with greatly enhanced mechanical properties is designed and fabricated to stabilize micro-silicon anodes. This biomimetic polymer can not only act as flexible “fibrils” in ligament, to adapt the high-volume change of silicon anode; but also act as “proteoglycan” in ligament to firmly hold these flexible fibrils and proactively constrain stress concentration of silicon anode. The combination of “soft to hard” hierarchical structure would endow binders with excellent elasticity and toughness. The pure micro-Si (5∼10 μm) electrodes with PSB binder exhibit high initial coulombic efficiency (ICE) of 93.3 % and favorable reversible capacity of ∼1500 mAh g−1 at 4000 mA g−1 after 600 cycles. Furthermore, the PSB binder also enables the μSi/GR//NCM811 full cell with 91.4 % capacity retention over 200 cycles. This functional PSB binders provide inspiration for constructing μSi anodes with high-ICE, high reversible capacity, and long-cycling life.

Bio-Inspired Self-Healing Silicon Anodes: Harnessing Tea Polyphenols to Enhance Lithium-Ion Battery Performance.

This study introduces an anode material for lithium-ion batteries, achieved by integrating tea polyphenols (TP) with the widely utilized polyacrylic acid (PAA) binder. The composite material capitalizes on the intrinsic self-healing properties of TP, enhancing the anode's durability and adhesiveness without the need for additional organic synthesis. The incorporation of TP has been demonstrated to significantly elevate ionic conductivity and expedite lithium ion diffusion, thereby reducing interfacial resistance and decelerating the rate of capacity fade due to electrolyte decomposition and silicon particle expansion. Employing a comprehensive analytical toolkit, including Fourier transform infrared spectroscopy, thermogravimetric analysis, peel strength measurements, and density functional theory calculations, we elucidated the physicochemical properties of the Si@PAA-TP anode. The anode's electrochemical performance was systematically assessed through galvanostatic charge-discharge, cyclic voltammetry, and electrochemical impedance spectroscopy, with scanning electron microscopy providing insights into postcycling mechanical property alterations. This research advances a cost-effective, high-performance adhesive strategy for silicon anodes and contributes to the development.

Electrochemical in-situ lithiated Li2SiO3 layer promote high performance silicon anode for lithium-ion batteries

Si anode is considered to be one of the most promising candidates for the next-generation lithium-ion batteries (LIBs). However, the severe volume variation of Si (> 300%) during the lithiation/delithiation process results in unstable interface and thus contributes to poor cycling stability. Moreover, the relatively low conductivity derived from the semiconductor nature of Si leads to inferior rate performance. Herein, Li2SiO3 layer with fast lithium-ions transport capability and high mechanical property was formed on Si surface in an in-situ electrochemical method. The relationships between the valence of SiOx and LixSiOy constituents were readily studied. Fortunately, the as-prepared Si@ES-LSO showed great potential to mitigate the expansion and high lithium-ions diffusion coefficient. When employed as anode materials for LIBs, the modified Si anode delivered a specific capacity of 2074.8 mAh g−1 at 1000 mA g−1 with a retention ratio of 98.9% after 100 cycles, demonstrating superior electrochemical performance. This work provides a facial and efficient strategy for the roadmap of Si anode application.

A 3D flexible conductive network skeleton by SWCNT-COOH and PVA-PAA enabling high performance for Si anode

Silicon anode undergoes dramatic volume expansion during charge and discharge, causing structural and interfacial instability that severely degrades battery cycling performance. Herein, we propose a three-dimensional (3D) flexible self-standing SiMP/SWCNT-COOH@PVA/PAA anode, in which carboxylation-modified single-walled carbon nanotubes (SWCNT-COOH) construct a highly conductive and flexible skeleton to provide rapid electron transport channels for micron silicon (SiMP), while polyacrylic acid-polyvinyl alcohol (PVA-PAA) cross-linking layer forms a high-strength polymer interface to strengthen the conductive skeleton and helps to maintain the structural integrity of SiMP. The resulting electrode exhibits ultra-high electrical conductance (12406 S m−1) and exceptional mechanical characteristic (tensile strength of 46.95 MPa). More importantly, it demonstrates extremely stable electrochemical properties, with an impressive maximum capacity of approximately 2868.5 mAh g−1 at 0.2C, while retaining an exceptional 96.49 % of capacity even after 100 cycles. A consistent capacity of 1000 mAh g−1 at 1C throughout 1000 cycles is also realized. Furthermore, a flexible full battery based on SiMP/SWCNT-COOH@PVA/PAA anode achieves a discharge capacity of 49.5 mAh g−1 following 100 cycles, and illuminates a LED strip normally under various bending conditions. These results are expected to open a new way towards enhanced performance silicon-based electrodes within flexible LIBs.

Silicon-air batteries enabled by in-situ FeMn alloy-catalyzed nitrogen-doped carbon nanotube arrays as efficient air electrodes catalysts

Silicon-air batteries (SABs) have become promising candidates for energy conversion and storage devices due to their high theoretical energy density, cost-effectiveness, and inherent safety. However, the slow kinetics of the 4e− transfer in the oxygen reduction reaction (ORR) at the cathode during discharge, coupled with severe polarization, reduces the battery’s capacity and hinders the development of silicon-air batteries. The cathodes of currently developed SABs primarily rely on commercial Pt/C and MnO2, with limited research on low-cost, efficient, and stable air cathodes for SABs. To address this issue, we synthesized nitrogen-doped carbon nanotubes containing FeMn alloy particles (FeMn@NCNTs) as cathode ORR catalysts using a simple high-temperature pyrolysis method combined with chemical vapor deposition. In an alkaline medium, the catalyst’s half-wave potential (E1/2) reached 0.83 V. Moreover, the FeMn@NCNTs air cathode exhibited excellent compatibility with the silicon anode, and the constructed aqueous silicon-air battery demonstrated a high specific capacity (165 Ah kg−1) and power density (3.69 mW cm−2). Additionally, the quasi-solid-state SABs constructed with FeMn@NCNTs showed stable operation over a wide temperature range, providing a new solution for the development of low-cost, efficient silicon-air batteries suitable for a wide range of applications.

Interaction of Boron-Based Cross-Linkers with Polymer Binders for Silicon Anodes in Lithium-Ion Batteries

Interaction of Boron-Based Cross-Linkers with Polymer Binders for Silicon Anodes in Lithium-Ion Batteries

Enhancing Electrochemical Performance of Si@CNT Anode by Integrating SrTiO3 Material for High-Capacity Lithium-Ion Batteries

Silicon (Si) has attracted worldwide attention for its ultrahigh theoretical storage capacity (4200 mA h g−1), low mass density (2.33 g cm−3), low operating potential (0.4 V vs. Li/Li+), abundant reserves, environmentally benign nature, and low cost. It is a promising high-energy-density anode material for next-generation lithium-ion batteries (LIBs), offering a replacement for graphite anodes owing to the escalating energy demands in booming automobile and energy storage applications. Unfortunately, the commercialization of silicon anodes is stringently hindered by large volume expansion during lithiation–delithiation, the unstable and detrimental growth of electrode/electrolyte interface layers, sluggish Li-ion diffusion, poor rate performance, and inherently low ion/electron conductivity. These present major safety challenges lead to quick capacity degradation in LIBs. Herein, we present the synergistic effects of nanostructured silicon and SrTiO3 (STO) for use as anodes in Li-ion batteries. Si and STO nanoparticles were incorporated into a multiwalled carbon nanotube (CNT) matrix using a planetary ball-milling process. The mechanical stress resulting from the expansion of Si was transferred via the CNT matrix to the STO. We discovered that the introduction of STO can improve the electrochemical performance of Si/CNT nanocomposite anodes. Experimental measurements and electrochemical impedance spectroscopy provide evidence for the enhanced mobility of Li-ions facilitated by STO. Hence, incorporating STO into the Si@CNT anode yields promising results, exhibiting a high initial Coulombic efficiency of approximately 85%, a reversible specific capacity of ~800 mA h g−1 after 100 cycles at 100 mA g−1, and a high-rate capability of 1400 mA g−1 with a capacity of 800 mA h g−1. Interestingly, it exhibits a capacity of 350 mAh g−1 after 1000 lithiation and delithiation cycles at a high rate of 600 mA hg−1. This result unveils and sheds light on the design of a scalable method for manufacturing Si anodes for next-generation LIBs.

Preparation of hard carbon–coated and metal-modified silicon anode materials for lithium-ion batteries

Preparation of hard carbon–coated and metal-modified silicon anode materials for lithium-ion batteries

Advances in Coating Materials for Silicon-Based Lithium-Ion Battery Anodes

Silicon anodes, which exhibit high theoretical capacity and very low operating potential, are promising as anode candidates that can satisfy the conditions currently required for secondary batteries. However, the low conductivity of silicon and the alloying/dealloying phenomena that occur during charging and discharging cause sizeable volume expansion with side reactions; moreover, various electrochemical issues result in inferior cycling performance. Therefore, many strategies have been proposed to mitigate these problems, with the most commonly used method being the use of nanosized silicon. However, this approach leads to another electrochemical limitation—that is, an increase in side reactions due to the large surface area. These problems can effectively be resolved using coating strategies. Therefore, to address the issues faced by silicon anodes in lithium-ion batteries, this review comprehensively discusses various coating materials and the related synthesis methods. In this review, the electrochemical properties of silicon-based anodes are outlined according to the application of various coating materials such as carbon, inorganic (including metal-, metal oxide-, and nitride-based) materials, and polymer. Additionally, double shells introduced using two materials for double coatings exhibit more complementary electrochemical properties than those of their single-layer counterparts. The strategy involving the application of a coating is expected to have a positive effect on the commercialization of silicon-based anodes.

Construction of WO3 nanowires artificial solid electrolyte interphase on silicon nanoparticles with sea urchin like structure for improving silicon anode stability

Giant volumetric variation of silicon during repeat lithiation/delethiation process leads to structure failure of silicon-based anodes and thus their initial high capacitance is hard to be maintained under long-run cyclic charging/discharging. Construction porous structure silicon composites and formation of artificial solid electrolyte interphase (SEI) coating on silicon particles are two effective ways to improve stability of silicon-based anodes. In this work, above two strategies are combined to construct a composite of inorganic artificial SEI WO3 nanowires/Si nanoparticles with sea urchin like porous structure via simple hydrothermal method. The silicon nanoparticles act as seeds for around 70 nm average diameter WO3 nanowires formation in compared with that of WO3 nano-rods around 500 nm diameter without Si nanoparticle seeds. The WO3 nanowire artificial SEI coating is found to be effective in preventing SEI overgrowth and their network provides spaces for volumetric variation of silicon nanoparticles in the bulk anode matrix during cyclic test, leading to reversible charging/discharging of stable bulk anode in compared with pure silicon anode of fast capacitance decay. The gravimetric capacitance of optimized composite reaches 1410.6 mAh·g−1 and its capacity remains 1039 mAh·g−1 after 200 cycles.

Polyacrylonitrile and aluminum metal dual functionalization interconnected network for superior lithium storage in silicon anode

Currently, silicon-based anode is one of the most promising anode materials that can be applied in next-generation lithium-ion batteries. However, the high activity of the electrode–electrolyte interface and low electronic conductivity of Si anode during the cycling process greatly limits its large-scale application. Aluminum (Al) is the metallic current collector known to promote electronic conductivity and lithium-ion transfer at low cost. However, to our knowledge, scalable interface engineering incorporating Al with carbonized polymer has not been reported. Herein, a polyacrylonitrile (PAN) and aluminum metal dual functionalization interconnected network is achieved via a simple sol-gel method followed by high-temperature calcination to obtain a stable solid electrolyte interphase (SEI) while allowing fast Li+ transmission. The calculated diffusion energy barrier for lithium ions in Al is 0.2198 eV, significantly lower than that in Cu and Fe. Benefiting from the enhanced interfacial protection and kinetics of Si with polyacrylonitrile/Al, the prepared Si@Al@CPAN anode exhibits high lithium storage capacity (2034.90 mAh/g after 150 cycles at 0.84 A/g). At the same time, the prepared Si@Al@CPAN anode outperforms the pure Si anode in rate performance at 12.6 A/g (1116.75 mAh/g vs. 2.84 mAh/g). The present work delivers new design ideas for high-performance Si anode with a multi-functionalization interface.