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.

Quantum confinement and its related effects on the critical size of GeO2 nanoparticles anodes for lithium batteries.

This work has been performed to determine the critical size of the GeO2 nanoparticle for lithium battery anode applications and identify its quantum confinement and its related effects on the electrochemical performance. GeO2 nanoparticles with different sizes of ∼ 2, ∼ 6, ∼ 10, and ∼ 35 nm were prepared by adjusting the reaction rate, controlling the reaction temperature and reactant concentration, and using different solvents. Among the different sizes of the GeO2 nanoparticles, the ∼ 6 nm sized GeO2 showed the best electrochemical performance. Unexpectedly smaller particles of the ∼ 2 nm sized GeO2 showed the inferior electrochemical performances compared to those of the ∼ 6 nm sized one. This was due to the low electrical conductivity of the ∼ 2 nm sized GeO2 caused by its quantum confinement effect, which is also related to the increase in the charge transfer resistance. Those characteristics of the smaller nanoparticles led to poor electrochemical performances, and their relationships were discussed.

Ultra-Thin Lithium Silicide Interlayer for Solid-State Lithium-Metal Batteries.

All-solid-state batteries with metallic lithium (LiBCC ) anode and solid electrolyte (SE) are under active development. However, an unstable SE/LiBCC interface due to electrochemical and mechanical instabilities hinders their operation. Herein, an ultra-thin nanoporous mixed ionic and electronic conductor (MIEC) interlayer (≈3.25 µm), which regulates LiBCC deposition and stripping, serving as a 3D scaffold for Li0 ad-atom formation, LiBCC nucleation, and long-range transport of ions and electrons at SE/LiBCC interface is demonstrated. Consisting of lithium silicide and carbon nanotubes, the MIEC interlayer is thermodynamically stable against LiBCC and highly lithiophilic. Moreover, its nanopores (<100 nm) confine the deposited LiBCC to the size regime where LiBCC exhibits "smaller is much softer" size-dependent plasticity governed by diffusive deformation mechanisms. The LiBCC thus remains soft enough not to mechanically penetrate SE in contact. Upon further plating, LiBCC grows in between the current collector and the MIEC interlayer, not directly contacting the SE. As a result, a full-cell having Li3.75 Si-CNT/LiBCC foil as an anode and LiNi0.8 Co0.1 Mn0.1 O2 as a cathode displays a high specific capacity of 207.8 mAh g-1 , 92.0% initial Coulombic efficiency, 88.9% capacity retention after 200 cycles (Coulombic efficiency reaches 99.9% after tens of cycles), and excellent rate capability (76% at 5 C).

Spinodal Decomposition Method for Structuring Germanium-Carbon Li-Ion Battery Anodes.

To increase the energy density of lithium-ion batteries (LIBs), high-capacity anodes which alloy with Li ions at a low voltage against Li/Li+ have been actively pursued. So far, Si has been studied the most extensively because of its high specific capacity and cost efficiency; however, Ge is an interesting alternative. While the theoretical specific capacity of Ge (1600 mAh g-1) is only half that of Si, its density is more than twice as high (Ge, 5.3 g cm-3; Si, 2.33 g cm-3), and therefore the charge stored per volume is better than that of Si. In addition, Ge has a 400 times higher ionic diffusivity and 4 orders of magnitude higher electronic conductivity compared to Si. However, similarly to Si, Ge needs to be structured in order to manage stresses induced during lithiation and many reports have achieved sufficient areal loadings to be commercially viable. In this work, spinodal decomposition is used to make secondary particles of about 2 µm in diameter that consist of a mixture of ∼30 nm Ge nanoparticles embedded in a carbon matrix. The secondary structure of these germanium-carbon particles allows for specific capacities of over 1100 mAh g-1 and a capacity retention of 91.8% after 100 cycles. Finally, high packing densities of ∼1.67 g cm-3 are achieved in blended electrodes by creating a bimodal size distribution with natural graphite.

Surface reduction in lithium- and manganese-rich layered cathodes for lithium ion batteries drives voltage decay.

Li- and Mn-rich layered oxides (Li1.2Ni0.2Mn0.6O2) are actively pursued as high energy and sustainable alternatives to the current Li-ion battery cathodes that contain Co. However, the severe decay in discharge voltage observed in these cathodes needs to be addressed before they can find commercial applications. A few mechanisms differing in origin have been proposed to explain the voltage fade, which may be caused by differences in material composition, morphology and electrochemical testing protocols. Here, these challenges are addressed by synthesising Li1.2Ni0.2Mn0.6O2 using three different hydrothermal and solid-state approaches and studying their degradation using the same cell design and cycling protocols. The voltage fade is found to be similar under the same electrochemical testing protocols, regardless of the synthesis method. X-ray absorption near edge, extended X-ray absorption fine structure spectroscopies, and energy loss spectroscopy in a scanning transmission electron microscope indicate only minor changes in the bulk Mn oxidation state but reveal a much more reduced particle surface upon extended cycling. No spinel phase is seen via the bulk structural characterisation methods of synchrotron X-ray diffraction, 7Li magic angle spinning solid state nuclear magnetic resonance and Raman spectroscopy. Thus, the voltage fade is believed to largely result from a heavily reduced particle surface. This hypothesis is further confirmed by galvanostatic intermittent titration technique analysis, which indicates that only very small shifts in equilibrium potential take place, in contrast to the overpotential which builds up after cycling. This suggests that a major source of the voltage decay is kinetic in origin, resulting from a heavily reduced particle surface with slow Li transport.

Calendering-Compatible Macroporous Architecture for Silicon-Graphite Composite toward High-Energy Lithium-Ion Batteries.

Porous strategies based on nanoengineering successfully mitigate several problems related to volume expansion of alloying anodes. However, practical application of porous alloying anodes is challenging because of limitations such as calendering incompatibility, low mass loading, and excessive usage of nonactive materials, all of which cause a lower volumetric energy density in comparison with conventional graphite anodes. In particular, during calendering, porous structures in alloying-based composites easily collapse under high pressure, attenuating the porous characteristics. Herein, this work proposes a calendering-compatible macroporous architecture for a Si-graphite anode to maximize the volumetric energy density. The anode is composed of an elastic outermost carbon covering, a nonfilling porous structure, and a graphite core. Owing to the lubricative properties of the elastic carbon covering, the macroporous structure coated by the brittle Si nanolayer can withstand high pressure and maintain its porous architecture during electrode calendering. Scalable methods using mechanical agitation and chemical vapor deposition are adopted. The as-prepared composite exhibits excellent electrochemical stability of >3.6 mAh cm-2 , with mitigated electrode expansion. Furthermore, full-cell evaluation shows that the composite achieves higher energy density (932 Wh L-1 ) and higher specific energy (333 Wh kg-1 ) with stable cycling than has been reported in previous studies.

Continuous-Flow Synthesis of Carbon-Coated Silicon/Iron Silicide Secondary Particles for Li-Ion Batteries.

The development of better Li-ion battery (LIB) electrodes requires an orchestrated effort to improve the active materials as well as the electron and ion transport in the electrode. In this paper, iron silicide is studied as an anode material for LIBs because of its higher conductivity and lower volume expansion compared to pure Si particles. In addition, carbon nanotubes (CNTs) can be synthesized from the surface of iron-silicides using a continuous flow coating process where precursors are first spray dried into micrometer-scale secondary particles and are then flown through a chemical vapor deposition (CVD) reactor. Some CNTs are formed inside the secondary particles, which are important for short-range electrical transport and good utilization of the active material. Surface-bound CNTs on the secondary particles may help establish a long-range conductivity. We also observed that these spherical secondary particles allow for better electrode coating quality, cyclability, and rate performance than unstructured materials with the same composition. The developed electrodes retain a gravimetric capacity of 1150 mAh/g over 300 cycles at 1A/g as well as a 43% capacity retention at a rate of 5 C. Further, blended electrodes with graphite delivered a 539 mAh/g with high electrode density (∼1.6 g/cm3) and areal capacity (∼3.5 mAh/cm2) with stable cycling performance.

Fabrication of Lamellar Nanosphere Structure for Effective Stress-Management in Large-Volume-Variation Anodes of High-Energy Lithium-Ion Batteries.

The use of high-capacity anode materials to overcome the energy density limits imposed by the utilization of low-theoretical-capacity conventional graphite has recently drawn increased attention. Until now, stress management (including strategies relying on size, surface coating, and free volume control) has been achieved by addressing the critical problems originating from significant anode volume expansion upon lithiation. However, commercially viable alternatives to graphite have not yet been found. A new stress-management strategy relying on the use of a lamellar nanosphere Si anode is proposed. Specifically, nanospheres comprising ≈50 nm Si nanoparticles encapsulated by SiOx /Si/SiOx /C layers with thicknesses of <20 nm per layer are synthesized via one-pot chemical vapor deposition in various atmospheres. SiOx is found to act as a stress management interlayer when it is located between Si and mitigates stress intensification on the surface layer, allowing nanospheres to maintain their morphological integrity and promoting the formation of a stable solid electrolyte interphase layer during cycling. When tested using an industrial protocol, a full cell comprising a nanosphere/graphite blended anode and a lithium cobalt oxide cathode achieve an average energy density of 2440.2 Wh L-1 (1.72 times higher than that of conventional graphite) with a capacity retention ratio of 80% after 101 cycles.

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.

A Ternary Ni46 Co40 Fe14 Nanoalloy-Based Oxygen Electrocatalyst for Highly Efficient Rechargeable Zinc-Air Batteries.

Replacing noble-metal-based oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) electrocatalysts is the key to developing efficient Zn-air batteries (ZABs). Here, a homogeneous ternary Ni46 Co40 Fe14 nanoalloy with a size distribution of 30-60 nm dispersed in a carbon matrix (denoted as C@NCF-900) as a highly efficient bifunctional electrocatalyst produced via supercritical reaction and subsequent heat treatment at 900 °C is reported. Among all the transition-metal-based electrocatalysts, the C@NCF-900 exhibits the highest ORR performance in terms of half-wave potential (0.93 V) in 0.1 m KOH. Moreover, C@NCF-900 exhibits negligible activity decay after 10 000 voltage cycles with minor reduction (0.006 V). In ZABs, C@NCF-900 outperforms the mixture of Pt/C 20 wt% and IrO2 , cycled over 100 h under 58% depth of discharge condition. Furthermore, density functional theory (DFT) calculations and in situ X-ray absorption spectroscopy strongly support the active sites and site-selective reaction as a plausible ORR/OER mechanism of C@NCF-900.

Highly Active Bifunctional Electrocatalysts for Oxygen Evolution and Reduction in Zn-Air Batteries.

To realize the full performance of Zn-air batteries, the co-presence of a highly efficient oxygen reduction reaction (ORR) and an oxygen evolution reaction (OER) in the system is critical. Although copper and nickel are known to be bifunctional catalysts for ORR and OER, sluggish reactions as a result of the exceptionally strong O=O bond on the metal surface make it difficult to achieve high system efficiency. In this study, a metal carbide layer (CuCx and NiCx ) on dendritic copper and nickel is fabricated by a facile electrodeposition process to provide efficient catalytic active sites with moderate binding energy for easy electron transfer in both the OER and the ORR. The dendritic structure provides an enriched catalytic surface and the protective metal carbide layer offers an appropriate O binding energy and durability of Zn-air batteries. Owing to the presence of the stable metal carbide surface on the dendritic metal, the CuCx /Cu and NiCx /Ni catalysts exhibited well-defined limiting current densities of -5.19 and -5.11 mA cm-2 , respectively, and improved ORR and OER activities with lower polarization than the corresponding metal catalysts. Density functional theory revealed a 0.74 eV decrease in the overpotential of NiCx /Ni-catalyzed OER reactions compared with Ni-catalyzed OER reactions. The experimental and theoretical results prove that carbide layers on dendritic metal surfaces can greatly improve the activity of ORR and OER bifunctional electrocatalysts for Zn-air batteries.

Zinc-Reduced Mesoporous TiOx Li-Ion Battery Anodes with Exceptional Rate Capability and Cycling Stability.

We demonstrate a unique synthetic route for oxygen-deficient mesoporous TiOx by a redox-transmetalation process by using Zn metal as the reducing agent. The as-obtained materials have significantly enhanced electronic conductivity; 20 times higher than that of as-synthesized TiO2 material. Moreover, electrochemical impedance spectroscopy (EIS) and galvanostatic intermittent titration technique (GITT) measurements are performed to validate the low charge carrier resistance of the oxygen-deficient TiOx . The resulting oxygen-deficient TiOx battery anode exhibits a high reversible capacity (∼180 mA h g-1 at a discharge/charge rate of 1 C/1 C after 400 cycles) and an excellent rate capability (∼90 mA h g-1 even at a rate of 10 C). Also, the full cell, which is coupled with a LiCoO2 cathode material, exhibits an outstanding rate capability (>75 mA h g-1 at a rate of 3.0 C) and maintains a reversible capacity of over 100 mA h g-1 at a discharge/charge of 1 C/1 C for 300 cycles.