Hollow Silicon Nanostructures via the Kirkendall Effect.

The Kirkendall effect is a simple, novel phenomenon that may be applied for the synthesis of hollow nanostructures with designed pore structures and chemical composition. We demonstrate the use of the Kirkendall effect for silicon (Si) and germanium (Ge) nanowires (NWs) and nanoparticles (NPs) via introduction of nanoscale surface layers of SiO2 and GeO2, respectively. Depending on the reaction time, Si and Ge atoms gradually diffuse outward through the oxide layers, with pore formation in the nanostructural cores. Through the Kirkendall effect, NWs and NPs were transformed into nanotubes (NTs) and hollow NPs, respectively. The mechanism of the Kirkendall effect was studied via quantum molecular dynamics calculations. The hollow products demonstrated better electrochemical performance than their solid counterparts because the pores developed in the nanostructures resulted in lower external pressures during lithiation.

Considering Critical Factors of Li-rich Cathode and Si Anode Materials for Practical Li-ion Cell Applications.

In order to keep pace with increasing energy demands for advanced electronic devices and to achieve commercialization of electric vehicles and energy-storage systems, improvements in high-energy battery technologies are required. Among the various types of batteries, lithium ion batteries (LIBs) are among the most well-developed and commercialized of energy-storage systems. LIBs with Si anodes and Li-rich cathodes are one of the most promising alternative electrode materials for next-generation, high-energy batteries. Si and Li-rich materials exhibit high reversible capacities of <2000 mAh g(-1) and >240 mAh g(-1) , respectively. However, both materials have intrinsic drawbacks and practical limitations that prevent them from being utilized directly as active materials in high-energy LIBs. Examples for Li-rich materials include phase distortion during cycling and side reactions caused by the electrolyte at the surface, and for Si, large volume changes during cycling and low conductivity are observed. Recent progress and important approaches adopted for overcoming and alleviating these drawbacks are described in this article. A perspective on these matters is suggested and the requirements for each material are delineated, in addition to introducing a full-cell prototype utilizing a Li-rich cathode and Si anode.

Superior long-term energy retention and volumetric energy density for Li-rich cathode materials.

Li-rich materials are considered the most promising for Li-ion battery cathodes, as high energy densities can be achieved. However, because an activation method is lacking for large particles, small particles must be used with large surface areas, a critical drawback that leads to poor long-term energy retention and low volumetric energy densities. Here we propose a new material engineering concept to overcome these difficulties. Our material is designed with 10 µm-sized secondary particles composed of submicron scaled flake-shaped primary particles that decrease the surface area without sacrificing rate capability. A novel activation method then overcomes the previous limits of Li-rich materials with large particles. As a result, we attained high average voltage and capacity retention in turn yielding excellent energy retention of 93% during 600 cycles. This novel and unique approach may furthermore open the door to new material engineering methods for high-performance cathode materials.

Flexible high-energy Li-ion batteries with fast-charging capability.

With the development of flexible mobile devices, flexible Li-ion batteries have naturally received much attention. Previously, all reported flexible components have had shortcomings related to power and energy performance. In this research, in order to overcome these problems while maintaining the flexibility, honeycomb-patterned Cu and Al materials were used as current collectors to achieve maximum adhesion in the electrodes. In addition, to increase the energy and power multishelled LiNi0.75Co0.11Mn0.14O2 particles consisting of nanoscale V2O5 and LixV2O5 coating layers and a LiδNi0.75-zCo0.11Mn0.14VzO2 doping layer were used as the cathode-anode composite (denoted as PNG-AES) consisting of amorphous Si nanoparticles (<20 nm) loaded on expanded graphite (10 wt %) and natural graphite (85 wt %). Li-ion cells with these three elements (cathode, anode, and current collector) exhibited excellent power and energy performance along with stable cycling stability up to 200 cycles in an in situ bending test.

Etched graphite with internally grown Si nanowires from pores as an anode for high density Li-ion batteries.

A novel architecture consisting of Si nanowires internally grown from porous graphite is synthesized by etching of graphite with a lamellar structure via a VLS (vapor-liquid-solid) process. This strategy gives the high electrode density of 1.5 g/cm(3), which is comparable with practical anode of the Li-ion battery. Our product demonstrates a high volumetric capacity density of 1363 mAh/cm(3) with 91% Coulombic efficiency and high rate capability of 568 mAh/cm(3) even at a 5C rate. This good electrochemical performance allows porous graphite to offer free space to accommodate the volume change of Si nanowires during cycling and the electron transport to efficiently be improved between active materials.

Additive-Derived Surface Modification of Cathodes in All-Solid-State Batteries: The Effect of Lithium Difluorophosphate- and Lithium Difluoro(oxalato)borate-Derived Coating Layers.

Sulfide-based electrolytes, with their high conductivity and formability, enable the construction of high-performance, all-solid-state batteries (ASSBs). However, the instability of the cathode-sulfide electrolyte interface limits the commercialization of these ASSBs. Surface modification of cathodes using the coating technique has been explored as an efficient approach to stabilize these interfaces. In this study, the additives lithium difluorophosphate (LiDFP) and lithium difluoro(oxalato)borate (LiDFOB) are used to fabricate stable cathode coatings via heat treatment. The low melting points of LiDFP and LiDFOB enable the formation of thin and uniform coating layers by a low-temperature heat treatment. All-solid-state cells containing LiDFP- and LiDFOB-coated cathodes show electrochemical performances significantly better than those comprising uncoated cathodes. Among all of the as-prepared coated cathodes, LiDFP-coated cathodes fabricated using a slightly lower temperature than the phase-transition temperature of LiDFP (320 °C) show the best discharge capacity, rate capability, and cyclic performance. Furthermore, cells comprising LiDFP-coated cathodes showed significantly low impedance. X-ray photoelectron spectroscopy and high-resolution transmission electron microscopy confirm the effectiveness of the LiDFP coating. LiDFP-coated cathodes minimized side-reactions during cycling, resulting in a significantly low cathode-surface degradation. Hence, this study highlights the efficiency of the proposed coating method and its potential to facilitate the commercialization of ASSBs. Overall, this study reports an effective technique to stabilize the cathode-electrolyte interface in sulfide-based ASSBs, which could expedite the practical implementation of these advanced energy-storage devices.

Silicon as the Anode Material for Multivalent-Ion Batteries: A First-Principles Dynamics Study.

Due to its huge capacity, Si is a promising anode material for practical applications in lithium-ion batteries. Here, using first-principles calculations, we study the applicability of the amorphous Si anode in multivalent-ion batteries, which are of great interest as candidates for post-lithium-ion batteries. Of the multivalent Mg2+, Ca2+, Zn2+, and Al3+ ions, only Mg2+ and Ca2+ are able to form Mg2.3Si and Ca2.5Si by alloying with Si, delivering very high capacities of 4390 and 4771 mA h g-1, respectively. Mg2.3Si has an 8% smaller capacity than Ca2.5Si, but its volume expansion ratio and ion diffusivity are ∼200% smaller and 3 orders of magnitude higher than those of Ca2.5Si, respectively. The capacity, volume expansion, and ion diffusion of Mg2.3Si are excellently high, moderately small, and fairly fast, respectively, when compared to those of Li3.7Si, Na0.75Si, and K1.1Si. The high performance of Mg2.3Si can be understood in terms of the coordination numbers of Si and the atomic size of Mg. This work suggests that, as a carrier ion for the amorphous Si anode, Mg2+ is the most competitive among the multivalent ions and is at least as good as monovalent ions.

Towards maximized volumetric capacity via pore-coordinated design for large-volume-change lithium-ion battery anodes.

To achieve the urgent requirement for high volumetric energy density in lithium-ion batteries, alloy-based anodes have been spotlighted as next-generation alternatives. Nonetheless, for the veritable accomplishment with regards to high-energy demand, alloy-based anodes must be evaluated considering several crucial factors that determine volumetric capacity. In particular, the electrode swelling upon cycling must be contemplated if these anodes are to replace conventional graphite anodes in terms of volumetric capacity. Herein, we propose macropore-coordinated graphite-silicon composite by incorporating simulation and mathematical calculation of numerical values from experimental data. This unique structure exhibits minimized electrode swelling comparable to conventional graphite under industrial electrode fabrication conditions. Consequently, this hybrid anode, even with high specific capacity (527 mAh g-1) and initial coulombic efficiency (93%) in half-cell, achieves higher volumetric capacity (493.9 mAh cm-3) and energy density (1825.7 Wh L-1) than conventional graphite (361.4 mAh cm-3 and 1376.3 Wh L-1) after 100 cycles in the full-cell configuration.

Fast-charging high-energy lithium-ion batteries via implantation of amorphous silicon nanolayer in edge-plane activated graphite anodes.

As fast-charging lithium-ion batteries turn into increasingly important components in forthcoming applications, various strategies have been devoted to the development of high-rate anodes. However, despite vigorous efforts, the low initial Coulombic efficiency and poor volumetric energy density with insufficient electrode conditions remain critical challenges that have to be addressed. Herein, we demonstrate a hybrid anode via incorporation of a uniformly implanted amorphous silicon nanolayer and edge-site-activated graphite. This architecture succeeds in improving lithium ion transport and minimizing initial capacity losses even with increase in energy density. As a result, the hybrid anode exhibits an exceptional initial Coulombic efficiency (93.8%) and predominant fast-charging behavior with industrial electrode conditions. As a result, a full-cell demonstrates a higher energy density (≥1060 Wh l-1) without any trace of lithium plating at a harsh charging current density (10.2 mA cm-2) and 1.5 times faster charging than that of conventional graphite.It is desirable to develop fast-charging batteries retaining high energy density. Here, the authors report a hybrid anode via incorporation of an implanted amorphous silicon nanolayer and edge-plane-activated graphite, which meets both criteria.

Challenges in Accommodating Volume Change of Si Anodes for Li-Ion Batteries.

Si has been considered as a promising alternative anode for next-generation Li-ion batteries (LIBs) because of its high theoretical energy density, relatively low working potential, and abundance in nature. However, Si anodes exhibit rapid capacity decay and an increase in the internal resistance, which are caused by the large volume changes upon Li insertion and extraction. This unfortunately limits their practical applications. Therefore, managing the total volume change remains a critical challenge for effectively alleviating the mechanical fractures and instability of solid-electrolyte-interphase products. In this regard, we review the recent progress in volume-change-accommodating Si electrodes and investigate their ingenious structures with significant improvements in the battery performance, including size-controlled materials, patterned thin films, porous structures, shape-preserving shell designs, and graphene composites. These representative approaches potentially overcome the large morphologic changes in the volume of Si anodes by securing the strain relaxation and structural integrity in the entire electrode. Finally, we propose perspectives and future challenges to realize the practical application of Si anodes in LIB systems.

Elastic a-silicon nanoparticle backboned graphene hybrid as a self-compacting anode for high-rate lithium ion batteries.

Although various Si-based graphene nanocomposites provide enhanced electrochemical performance, these candidates still yield low initial coloumbic efficiency, electrical disconnection, and fracture due to huge volume changes after extended cycles lead to severe capacity fading and increase in internal impedance. Therefore, an innovative structure to solve these problems is needed. In this study, an amorphous (a) silicon nanoparticle backboned graphene nanocomposite (a-SBG) for high-power lithium ion battery anodes was prepared. The a-SBG provides ideal electrode structures-a uniform distribution of amorphous silicon nanoparticle islands (particle size <10 nm) on both sides of graphene sheets-which address the improved kinetics and cycling stability issues of the silicon anodes. a-Si in the composite shows elastic behavior during lithium alloying and dealloying: the pristine particle size is restored after cycling, and the electrode thickness decreases during the cycles as a result of self-compacting. This noble architecture facilitates superior electrochemical performance in Li ion cells, with a specific energy of 468 W h kg(-1) and 288 W h kg(-1) under a specific power of 7 kW kg(-1) and 11 kW kg(-1), respectively.

Novel design of ultra-fast Si anodes for Li-ion batteries: crystalline Si@amorphous Si encapsulating hard carbon.

Nanocrystalline Si (c-Si) dispersed in amorphous Si (a-Si) encapsulating hard carbon (HC) has been synthesized as an anode material for fast chargeable lithium-ion batteries. The HC derived from natural polysaccharide was coated by a thin a-Si layer through chemical vapour deposition (CVD) using silane (SiH4) as a precursor gas. The HC@c-Si@a-Si anodes showed an excellent cycle retention of 97.8% even after 200 cycles at a 1 C discharge/charge rate. Furthermore, a high capacity retention of ∼54% of its initial reversible capacity at 0.2 C rate was obtained at a high discharge/charge rate of 5 C. Moreover, the LiCoO2/HC@c-Si@a-Si full-cell showed excellent rate capability and very stable long-term cycle. Even at a rate of 10 C discharge/charge, the capacity retention of the LiCoO2/HC@c-Si@a-Si full-cell was 50.8% of its capacity at a rate of 1 C discharge/charge and showed a superior cycle retention of 80% after 160 cycles at a rate of 1 C discharge/charge.