Orientation-dependent interfacial mobility governs the anisotropic swelling in lithiated silicon nanowires

Recent independent experiments demonstrated that the lithiation-induced volume expansion in silicon nanowires, nanopillars, and microslabs is highly anisotropic, with predominant expansion along the <110> direction but negligibly small expansion along the <111> direction. The origin of such anisotropic behavior remains elusive. Here, we develop a chemomechanical model to study the phase evolution and morphological changes in lithiated silicon nanowires. The model couples the diffusive reaction of lithium with the lithiation-induced elasto-plastic deformation. We show that the apparent anisotropic swelling is critically controlled by the orientation-dependent mobility of the core-shell interface, i.e., the lithiation reaction rate at the atomically sharp phase boundary between the crystalline core and the amorphous shell. Our results also underscore the importance of structural relaxation by plastic flow behind the moving phase boundary, which is essential to quantitative prediction of the experimentally observed morphologies of lithiated silicon nanowires. The study sheds light on the lithiation-mediated failure in nanowire-based electrodes, and the modeling framework provides a basis for simulating the morphological evolution, stress generation, and fracture in high-capacity electrodes for the next-generation lithium-ion batteries.     

Novel size and surface oxide effects in silicon nanowires as lithium battery anodes

With its high specific capacity, silicon is a promising anode material for high-energy lithium-ion batteries, but volume expansion and fracture during lithium reaction have prevented implementation. Si nanostructures have shown resistance to fracture during cycling, but the critical effects of nanostructure size and native surface oxide on volume expansion and cycling performance are not understood. Here, we use an ex situ transmission electron microscopy technique to observe the same Si nanowires before and after lithiation and have discovered the impacts of size and surface oxide on volume expansion. For nanowires with native SiO(2), the surface oxide can suppress the volume expansion during lithiation for nanowires with diameters <～50 nm. Finite element modeling shows that the oxide layer can induce compressive hydrostatic stress that could act to limit the extent of lithiation. The understanding developed herein of how volume expansion and extent of lithiation can depend on nanomaterial structure is important for the improvement of Si-based anodes.     

Kinetics of initial lithiation of crystalline silicon electrodes of lithium-ion batteries

Electrochemical experiments were conducted on {100}, {110}, and {111} silicon wafers to characterize the kinetics of the initial lithiation of crystalline Si electrodes. Under constant current conditions, we observed constant cell potentials for all orientations, indicating the existence of a phase boundary that separates crystalline silicon from the amorphous lithiated phase. For a given potential, the velocity of this boundary was found to be faster for {110} silicon than for the other two orientations. We show that our measurements of varying phase boundary velocities can accurately account for anisotropic morphologies and fracture developed in crystalline silicon nanopillars. We also present a kinetic model by considering the redox reaction at the electrolyte/lithiated silicon interface, diffusion of lithium through the lithiated phase, and the chemical reaction at the lithiated silicon/crystalline silicon interface. From this model, we quantify the rates of the reactions at the interfaces and estimate a lower bound on the diffusivity through the lithiated silicon phase.     

Graphene‐Bonded and ‐Encapsulated Si Nanoparticles for Lithium Ion Battery Anodes

Silicon (Si) has been considered a very promising anode material for lithium ion batteries due to its high theoretical capacity. However, high‐capacity Si nanoparticles usually suffer from low electronic conductivity, large volume change, and severe aggregation problems during lithiation and delithiation. In this paper, a unique nanostructured anode with Si nanoparticles bonded and wrapped by graphene is synthesized by a one‐step aerosol spraying of surface‐modified Si nanoparticles and graphene oxide suspension. The functional groups on the surface of Si nanoparticles (50–100 nm) not only react with graphene oxide and bind Si nanoparticles to the graphene oxide shell, but also prevent Si nanoparticles from aggregation, thus contributing to a uniform Si suspension. A homogeneous graphene‐encapsulated Si nanoparticle morphology forms during the aerosol spraying process. The open‐ended graphene shell with defects allows fast electrochemical lithiation/delithiation, and the void space inside the graphene shell accompanied by its strong mechanical strength can effectively accommodate the volume expansion of Si upon lithiation. The graphene shell provides good electronic conductivity for Si nanoparticles and prevents them from aggregating during charge/discharge cycles. The functionalized Si encapsulated by graphene sample exhibits a capacity of 2250 mAh g^?1 (based on the total mass of graphene and Si) at 0.1C and 1000 mAh g^?1 at 10C, and retains 85% of its initial capacity even after 120 charge/discharge cycles. The exceptional performance of graphene‐encapsulated Si anodes combined with the scalable and one‐step aerosol synthesis technique makes this material very promising for lithium ion batteries.     

The development of <100> texture in Fe-Cr-Co-Mo permanentmagnet alloys

The cold-rolled and recrystallization textures of Fe-Cr-Co-Mo permanent magnet alloys are described. The studied composition is Fe-30%Cr-15%Co-3%Mo (in wt.%). The cold-rolled texture can be considered to be {111}<110>, {111}<112>, {100}<110>, and {211}<110>, while the recrystallization texture can be considered to be {111}<100>, {110}<112>, {211}<110>, and {110}<110>. The secondary recrystallization is caused by heat-treating the alloys in the sequence of α, α+γ, α+γ+σ, α phase region. This results in a favorable texture of {110}<110> and <100> direction, aligning along the transverse direction (TD) of the strips. The best magnetic properties obtained in this study were 1.2 T (12.0 kG), iH _c=82.0 kAm^-1 (1025 Oe), and (BH)max= 60.8 kJm^-3 (7.6 MGOe) with TD alloys     

Formation of epitaxial NiSi2 nanowires on Si(100) surface by atomic force microscope nanolithography

Ni nanowries were fabricated by atomic force microscope nanolithography, evaporation, lift-off and annealing processes. Epitaxial NiSi2 nanowires on a Si(100) surface along Si(110) and (100) directions were formed by the rapid thermal annealing treatment of the Ni nanowires at 400 degrees C. The silicide nanowires along the Si(110) direction had coherent type-A Si(111) and Si(100) interfaces, while those along the Si(100) direction had a type-A Si(110) interface. Silicide nanowires were agglomerated when the Ni nanowires were annealed at high temperature (> or = 500 degrees C). The mechanism of formation of a faceted nanowire was discussed based on the minimization of the total surface energy.     

Core–Shell Si/C Nanospheres Embedded in Bubble Sheet‐like Carbon Film with Enhanced Performance as Lithium Ion Battery Anodes

Due to its high theoretical capacity and low lithium insertion voltage plateau, silicon has been considered one of the most promising anodes for high energy and high power density lithium ion batteries (LIBs). However, its rapid capacity degradation, mainly caused by huge volume changes during lithium insertion/extraction processes, remains a significant challenge to its practical application. Engineering Si anodes with abundant free spaces and stabilizing them by incorporating carbon materials has been found to be effective to address the above problems. Using sodium chloride (NaCl) as a template, bubble sheet‐like carbon film supported core–shell Si/C composites are prepared for the first time by a facile magnesium thermal reduction/glucose carbonization process. The capacity retention achieves up to 93.6% (about 1018 mAh g^?1) after 200 cycles at 1 A g^?1. The good performance is attributed to synergistic effects of the conductive carbon film and the hollow structure of the core–shell nanospheres, which provide an ideal conductive matrix and buffer spaces for respectively electron transfer and Si expansion during lithiation process. This unique structure decreases the charge transfer resistance and suppresses the cracking/pulverization of Si, leading to the enhanced cycling performance of bubble sheet‐like composite.     

Self-assembled shape- and orientation-controlled synthesis of nanoscale Cu3Si triangles, squares, and wires

Controlling shape and orientation is important for the synthesis of functional nanomaterials. In this work, nanoscale Cu3Si triangles, squares, and wires have been grown on Si(111), (100), and (110) substrates, respectively, through a template-free Au-nanoparticle-assisted vapor transport method. The sides of nanotriangles and nanosquares and the growth direction of the nanowires are all along Si <110>, giving rise to long-range ordering of the nanostructures. Au nanoparticles absorb Cu vapor and facilitate the rate-limited diffusion of Si, which is critical for the shape-controlled growth of Cu3Si. This bottom-up approach to synthesize shape- and orientation-controlled Cu3Si nanostructures might be applicable to the tailored growth of other materials.     

Rationally Designed Silicon Nanostructures as Anode Material for Lithium‐Ion Batteries

Silicon (Si) is promising for high capacity anodes in lithium‐ion batteries due to its high theoretical capacity, low working potential, and natural abundance. However, there are two main drawbacks that impede its further practical applications. One is the huge volume expansion generating during lithiation and delithiation progresses, which leads to severe structural pulverization and subsequently rapid capacity fading of the electrode. The other is the relatively low intrinsic electronic conductivity, therefore, seriously impacting the rate performance. In the past decades, numerous efforts have been devoted for improving the cycling stability and rate capability by rational designs of different nanostructures of Si materials and incorporations with some conductive agents. In this review, the authors summarize the exciting recent research works and focus on not only the synthesis techniques, but also the composition strategies of silicon nanostructures. The advantages and disadvantages of the nanostructures as well as the perspective of this research field are also discussed. We aim to give some reference for engineering application on Si anodes in lithium ion batteries.     

Si/C particles on graphene sheet as stable anode for lithium-ion batteries

Silicon is considered as one of the most promising anodes for Li-ion batteries (LIBs),but it is limited for commercial applications by the critical issue of large volume expansion during the lithiation.In this work,the structure of silicon/carbon (Si/C) particles on graphene sheets (Si/C-G) was obtained to solve the issue by using the void space of Si/C particles and graphene.Si/C-G material was from Si/PDA-GO that silicon particles was coated by polydopamine (PDA) and reacted with oxide graphene (GO).The Si/C-G material have good cycling performance as the stability of the structure during the lithiation/dislithiation.The Si/C-G anode materials exhibited high reversible capacity of 1910.5 mA h g-1 and 1196.1 mA h g-1 after 700 cycles at 357.9 mA g-1,and have good rate property of 507.2 mA h g-1 at high current density,showing significantly improved commercial viability of silicon electrodes in high-energy-density LIBs.     

Gas-source molecular beam epitaxy of Si(111) on Si(110) substrates by insertion of 3C-SiC(111) interlayer for hybrid orientation technology

A method to realize a novel hybrid orientations of Si surfaces, Si(111) on Si(110), has been developed by use of a Si(111)/3C-SiC(111)/Si(110) trilayer structure. This technology allows us to use the Si(111) portion for the n-type and the Si(110) portion for the p-type channels, providing a solution to the current drive imbalance between the two channels confronted in Si(100)-based complementary metal oxide semiconductor (CMOS) technology. The central idea is to use a rotated heteroepitaxy of 3C-SiC(111) on Si(110) substrate, which occurs when a 3C-SiC film is grown under certain growth conditions. Monomethylsilane (SiH₃-CH₃) gas-source molecular beam epitaxy (GSMBE) is used for this 3C-SiC interlayer formation while disilane (Si₂H₆) is used for the top Si(111) layer formation. Though the film quality of the Si epilayer leaves a lot of room for betterment, the present results may suffice to prove its potential as a new technology to be used in the next generation CMOS devices.     

Strain Regulating and Kinetics Accelerating of Micro-Sized Silicon Anodes via Dual-Size Hollow Graphitic Carbons Conductive Additives

Micro-sized silicon (µSi) anode features fewer interfacial side reactions and lower costs compared to nanosized silicon, and has higher commercial value when applied as a lithium-ion battery (LIB) anode. However, the high localized stress generated during (de)lithiation causes electrode breakdown and performance deterioration of the µSi anode. In this work, hollow graphitic carbons with tailored dual sizes are employed as conductive additives for the µSi anode to overcome electrode failure. The dual-size hollow graphitic carbons (HGC) additives consist of particles with micrometer size similar to the µSi particles; these additives are used for strain regulation. Additionally, nanometer-size particles similar to commercial carbon black Spheron (SP) are used mainly for kinetics acceleration. In addition to building an efficient conductive network, the dual-size hollow graphitic carbon conductive additive prevents the fracture of the electrode by reducing local stress and alleviating volume expansion. The µSi anode with dual-size hollow graphitic carbons as conductive additives achieves an impressive capacity of 651.4 mAh g⁻¹ after 500 cycles at a high current density of 2 A g⁻¹. These findings suggest that dual-size hollow graphitic carbons are expected to be superior conductive additives for micro-sized alloy anodes similar to µSi.     

HWCVD MoO3 nanoparticles and a-Si for next generation Li-ion anodes

We have employed hot wire chemical vapor deposition (HWCVD) for the generation of MoO₃ nanostructures at high density. Furthermore, the morphology of the nanoparticles is easily tailored by altering the HWCVD synthesis conditions. The MoO₃ nanoparticles have been demonstrated as high-capacity Li-ion battery anodes for next-generation electric vehicles. Specifically, the MoO₃ anodes have been shown to have approximately three times the Li-ion capacity of commercially employed graphite anodes in thick electrodes suitable for vehicular applications. However because the materials are high volume expansion materials (≥ 100%), conformal Al₂O₃ coatings deposited with atomic layer deposition (ALD) were required before high rate capability was demonstrated. Recently, NREL is exploring high capacity Si anode materials that have a volume expansion of ~ 400%. It is assumed that new ALD coatings will need to be developed in order to stabilize Si as an anode material. Silicon is a superior choice for an anode material to the metal oxide structures due to both a higher capacity and a significantly lower hysteresis in the voltage vs. Li/Li⁺ for the charge/discharge profiles.     

Effects of Geometry and Shape on the Mechanical Behaviors of Silicon Nanowires

Molecular dynamics simulations have been performed to investigate the effects of cross section geometry and shape on the mechanical behaviors of silicon nanowires (Si NWs) under tensile loading. The results show that elasticity of <100> rectangular Si NWs depends on their cross section aspect ratios while the elastic limits of <110> and <111> wires show geometry independence. Despite the significant influence of axial orientation, both yield stress and Young's Modulus show the remarkable shape dependence for wires with various regular cross sections. Additionally, underlying mechanism for the geometry and shape effects on mechanical behavior are discussed based on the fundamental energy theory. From energy view, edge energy is the crucial factor that determines shape dependence of the elastic limits.     

Self-Repairable Silicon Anodes Using a Multifunctional Binder for High-Performance Lithium-Ion Batteries

Despite of extremely high theoretical capacity of Si (3579 mAh g⁻¹), Si anodes suffer from pulverization and delamination of the electrodes induced by large volume change during charge/discharge cycles. To address those issues, herein, self-healable and highly stretchable multifunctional binders, polydioxythiophene:polyacrylic acid:phytic acid (PEDOT:PAA: PA, PDPP) that provide Si anodes with self-healability and excellent structural integrity is designed. By utilizing the self-healing binder, Si anodes self-repair cracks and damages of Si anodes generated during cycling. For the first time, it is demonstrated that Si anodes autonomously self-heal artificially created cracks in electrolytes under practical battery operating conditions. Consequently, this self-healable Si anode can still deliver a reversible capacity of 2312 mAh g⁻¹ after 100 cycles with remarkable initial Coulombic efficiency of 94%, which is superior to other reported Si anodes. Moreover, the self-healing binder possesses enhanced Li-ion diffusivity with additional electronic conductivity, providing excellent rate capability with a capacity of 2084 mAh g⁻¹ at a very high C-rate of 5 C.     

Exploring Critical Factors Affecting Strain Distribution in 1D Silicon‐Based Nanostructures for Lithium‐Ion Battery Anodes

Despite the advantage of high capacity, the practical use of the silicon anode is still hindered by large volume expansion during the severe pulverization lithiation process, which results in electrical contact loss and rapid capacity fading. Here, a combined electrochemical and computational study on the factor for accommodating volume expansion of silicon‐based anodes is shown. 1D silicon‐based nanostructures with different internal spaces to explore the effect of spatial ratio of voids and their distribution degree inside the fibers on structural stability are designed. Notably, lotus‐root‐type silicon nanowires with locally distributed void spaces can improve capacity retention and structural integrity with minimum silicon pulverization during lithium insertion and extraction. The findings of this study indicate that the distribution of buffer spaces, electrochemical surface area, as well as Li diffusion property significantly influence cycle performance and rate capability of the battery, which can be extended to other silicon‐based anodes to overcome large volume expansion.     

CVD金刚石的晶体形态及界面位向关系

综述了CVD金刚石的晶体形态及界面位向关系.用SEM观察CVD金刚石晶粒形态主要有立方体、长方体、八面体、立方八面体、孪晶八面体、十面体和二十面体颗粒以及球形金刚石,讨论了晶粒的形成条件.用TEM观察则主要有单晶体、孪晶八面体和五重孪晶体形态.界面位向关系主要有:Si(001)//Diamond(001),Si<110>//Diamond<110(50078018);Si(111)//Diamond(111),Si<110>//Diamond<110>和Si(110)//Diamond(110),Si[110]//Diamond[111].     

Quantum growth of magnetic nanoplatelets of Co on Si with high blocking temperature

Self-organized Co nanoplatelets with a singular height, quantized lateral sizes, and unique shape and orientation have been fabricated on a template consisting of ordered Al nanocluster arrays on Si(111)-7 x 7 surfaces. Despite their small volume (a few nm(3)), these nanomagnets exhibit an unusually high blocking temperature (>100 K). The perpendicular direction for easy magnetization, the high blocking temperature, the size tunability, and the epitaxial growth on Si substrates make these nanomagnets important for applications in information technology.     

Surface Coating Constraint Induced Anisotropic Swelling of Silicon in Si–Void@SiO x Nanowire Anode for Lithium‐Ion Batteries

Here a simple and an environmentally friendly approach is developed for the fabrication of Si–void@SiO_x nanowires of a high‐capacity Li‐ion anode material. The outer surface of the robust SiO_x backbone and the inside void structure in Si–void@SiO_x nanowires appropriately suppress the volume expansion and lead to anisotropic swelling morphologies of Si nanowires during lithiation/delithiation, which is first demonstrated by the in situ lithiation process. Remarkably, the Si–void@SiO_x nanowire electrode exhibits excellent overall lithium‐storage performance, including high specific capacity, high rate property, and excellent cycling stability. A reversible capacity of 1981 mAh g^?1 is obtained in the fourth cycle, and the capacity is maintained at 2197 mAh g^?1 after 200 cycles at a current density of 0.5 C. The outstanding overall properties of the Si–void@SiO_x nanowire composite make it a promising anode material of lithium‐ion batteries for the power‐intensive energy storage applications.     

Origin of diameter-dependent growth direction of silicon nanowires

A nucleation thermodynamic model was developed to clarify the diameter-dependent crystallographic orientation of silicon nanowires (SiNWs) grown via the vapor-liquid-solid (VLS) mechanism with an Au catalyst. The calculated critical energies (E(r*)) and corresponding critical radii (r*) of the SiNWs with <111> and <110> orientations as a function of Au-catalyst size (D(Au)) revealed that the 110-oriented SiNW with r is preferred below D(Au) = approximately 25 nm, but the preferred direction changes to <111> above D(Au) = approximately 25 nm. The model indicated that the nucleated SiNW with a radius (r) above r is stable and continues to grow until the diameter becomes equal to D(Au) but that the crystallographic orientation is maintained. Thus, the predicted growth direction of the final SiNW with a size of D(Au) is <110> for D(Au) < approximately 25 nm and <111> for D(Au) > approximately 25 nm, which is in excellent agreement with reported experimental results.