Germanium tin alloy nanowires as anode materials for high performance Li-ion batteries.

The combination of two active Li-ion materials (Ge and Sn) can result in improved conduction paths and higher capacity retention. Here we report for the first time, the implementation of Ge1-x Sn x alloy nanowires as anode materials for Li-ion batteries. Ge1-x Sn x alloy nanowires have been successfully grown via vapor-liquid-solid technique directly on stainless steel current collectors. Ge1-x Sn x (x = 0.048) nanowires were predominantly seeded from the Au0.80Ag0.20 catalysts with negligible amount of growth was also directly catalyzed from stainless steel substrate. The electrochemical performance of the the Ge1-x Sn x nanowires as an anode material for Li-ion batteries was investigated via galvanostatic cycling and detailed analysis of differential capacity plots (DCPs). The nanowire electrodes demonstrated an exceptional capacity retention of 93.4% from the 2nd to the 100th charge at a C/5 rate, while maintaining a specific capacity value of ∼921 mAh g-1 after 100 cycles. Voltage profiles and DCPs revealed that the Ge1-x Sn x nanowires behave as an alloying mode anode material, as reduction/oxidation peaks for both Ge and Sn were observed, however it is clear that the reversible lithiation of Ge is responsible for the majority of the charge stored.

Evaluating the Surface Chemistry of Black Phosphorus during Ambient Degradation.

Black phosphorus (BP) is emerging as a promising candidate for electronic, optical, and energy storage applications. However, its poor ambient stability remains a critical challenge. Evaluation of few-layer liquid-exfoliated BP during ambient exposure using X-ray photoelectron spectroscopy and attenuated total reflectance Fourier transform infrared spectroscopy allows its surface chemistry to be investigated. Oxidation of liquid-exfoliated few-layer BP initially occurs through nonbridging oxide species, which convert to bridging oxide species after ambient exposure. We demonstrate the instability of these bridging oxide species, which undergo hydrolysis to form volatile phosphorus oxides and evaporate from the BP surface. FTIR spectroscopy, scanning transmission electron microscopy, and atomic force microscopy were used to confirm the formation of liquid oxides through a continuous oxidation cycle that results in the decomposition of BP. Furthermore, we show that the instability of few-layer BP originates from the formation of bridging oxide species.

Large Block Copolymer Self-Assembly for Fabrication of Subwavelength Nanostructures for Applications in Optics.

Nanostructured surfaces are common in nature and exhibit properties such as antireflectivity (moth eyes), self-cleaning (lotus leaf), iridescent colors (butterfly wings), and water harvesting (desert beetles). We now understand such properties and can mimic some of these natural structures in the laboratory. However, these synthetic structures are limited since they are not easily mass produced over large areas due to the limited scalability of current technologies such as UV-lithography, the high cost of infrastructure, and the difficulty in nonplanar surfaces. Here, we report a solution process based on block copolymer (BCP) self-assembly to fabricate subwavelength structures on large areas of optical and curved surfaces with feature sizes and spacings designed to efficiently scatter visible light. Si nanopillars (SiNPs) with diameters of ∼115 ± 19 nm, periodicity of 180 ± 18 nm, and aspect ratio of 2-15 show a reduction in reflectivity by a factor of 100, <0.16% between 400 and 900 nm at an angle of incidence of 30°. Significantly, the reflectivity remains below 1.75% up to incident angles of 75°. Modeling the efficiency of a SiNP PV suggests a 24.6% increase in efficiency, representing a 3.52% (absolute) or 16.7% (relative) increase in electrical energy output from the PV system compared to AR-coated device.

Growing Oxide Nanowires and Nanowire Networks by Solid State Contact Diffusion into Solution-Processed Thin Films.

New techniques to directly grow metal oxide nanowire networks without the need for initial nanoparticle seed deposition or postsynthesis nanowire casting will bridge the gap between bottom-up formation and top-down processing for many electronic, photonic, energy storage, and conversion technologies. Whether etched top-down, or grown from catalyst nanoparticles bottom-up, nanowire growth relies on heterogeneous material seeds. Converting surface oxide films, ubiquitous in the microelectronics industry, to nanowires and nanowire networks by the incorporation of extra species through interdiffusion can provide an alternative deposition method. It is shown that solution-processed thin films of oxides can be converted and recrystallized into nanowires and networks of nanowires by solid-state interdiffusion of ionic species from a mechanically contacted donor substrate. NaVO3 nanowire networks on smooth Si/SiO2 and granular fluorine-doped tin oxide surfaces can be formed by low-temperature annealing of a Na diffusion species-containing donor glass to a solution-processed V2 O5 thin film, where recrystallization drives nanowire growth according to the crystal habit of the new oxide phase. This technique illustrates a new method for the direct formation of complex metal oxide nanowires on technologically relevant substrates, from smooth semiconductors, to transparent conducting materials and interdigitated device structures.

2D and 3D photonic crystal materials for photocatalysis and electrochemical energy storage and conversion.

This perspective reviews recent advances in inverse opal structures, how they have been developed, studied and applied as catalysts, catalyst support materials, as electrode materials for batteries, water splitting applications, solar-to-fuel conversion and electrochromics, and finally as photonic photocatalysts and photoelectrocatalysts. Throughout, we detail some of the salient optical characteristics that underpin recent results and form the basis for light-matter interactions that span electrochemical energy conversion systems as well as photocatalytic systems. Strategies for using 2D as well as 3D structures, ordered macroporous materials such as inverse opals are summarized and recent work on plasmonic-photonic coupling in metal nanoparticle-infiltrated wide band gap inverse opals for enhanced photoelectrochemistry are provided.

Electrochemical investigation of the role of MnO2 nanorod catalysts in water containing and anhydrous electrolytes for Li-O2 battery applications.

The electrochemical behaviour of MnO2 nanorod and Super P carbon based Li-O2 battery cathodes in water-containing sulfolane and anhydrous DMSO electrolytes are shown to be linked to specific discharge product formation. During discharge, large layered spherical agglomerates of LiOH were characteristically formed on the MnO2 cathodes while smaller, toroidal, spherical Li2O2 particles and films were formed on the Super P cathodes. In an anhydrous DMSO based electrolyte the LiOH structures were also found on cathodes discharged in the anhydrous electrolyte, suggesting that MnO2 initiates electrochemical decomposition of the DMSO electrolyte to form LiOH via H2O reactions with Li2O2. The LiOH crystals are uniquely formed on MnO2, and segregated to this phase even in mixed oxide-carbon cathodes. In contrast, no Li2O2 toroids were noted on Super P cathodes discharged in the DMSO based electrolytes. Instead, the morphology varied from smaller sheets (at high discharge current) to much larger agglomerates (at low discharge currents). In mixed carbon-MnO2 nanorod cathodes, the use of PVDF initiates H2O formation that affects discharge products and an overall mechanism governing phase formation at MnO2 in sulfolane and anhydrous DMSO with and without PVDF binder is presented. This work highlights the importance of careful consideration of electrolyte-cathode material-discharge product interactions in the search for more stable Li-O2 systems.

Recent progress in theoretical and computational investigations of Li-ion battery materials and electrolytes.

There is an increasing worldwide demand for high energy density batteries. In recent years, rechargeable Li-ion batteries have become important power sources, and their performance gains are driving the adoption of electrical vehicles (EV) as viable alternatives to combustion engines. The exploration of new Li-ion battery materials is an important focus of materials scientists and computational physicists and chemists throughout the world. The practical applications of Li-ion batteries and emerging alternatives may not be limited to portable electronic devices and circumventing hurdles that include range anxiety and safety among others, to their widespread adoption in EV applications in the future requires new electrode materials and a fuller understanding of how the materials and the electrolyte chemistries behave. Since this field is advancing rapidly and attracting an increasing number of researchers, it is crucial to summarise the current progress and the key scientific challenges related to Li-ion batteries from theoretical point of view. Computational prediction of ideal compounds is the focus of several large consortia, and a leading methodology in designing materials and electrolytes optimized for function, including those for Li-ion batteries. In this Perspective, we review the key aspects of Li-ion batteries from theoretical perspectives: the working principles of Li-ion batteries, the cathodes, anodes, and electrolyte solutions that are the current state of the art, and future research directions for advanced Li-ion batteries based on computational materials and electrolyte design.

High-performance germanium nanowire-based lithium-ion battery anodes extending over 1000 cycles through in situ formation of a continuous porous network.

Here we report the formation of high-performance and high-capacity lithium-ion battery anodes from high-density germanium nanowire arrays grown directly from the current collector. The anodes retain capacities of ∼ 900 mAh/g after 1100 cycles with excellent rate performance characteristics, even at very high discharge rates of 20-100C. We show by an ex situ high-resolution transmission electron microscopy and high-resolution scanning electron microscopy study that this performance can be attributed to the complete restructuring of the nanowires that occurs within the first 100 cycles to form a continuous porous network that is mechanically robust. Once formed, this restructured anode retains a remarkably stable capacity with a drop of only 0.01% per cycle thereafter. As this approach encompasses a low energy processing method where all the material is electrochemically active and binder free, the extended cycle life and rate performance characteristics demonstrated makes these anodes highly attractive for the most demanding lithium-ion applications such as long-range battery electric vehicles.

Germanium oxide removal by citric acid and thiol passivation from citric acid-terminated Ge(100).

Many applications of germanium (Ge) are underpinned by effective oxide removal and surface passivation. This important surface treatment step often requires H-X (X = Cl, Br, I) or HF etchants. Here, we show that aqueous citric acid solutions are effective in the removal of GeOx. The stability of citric acid-treated Ge(100) is compared to HF and HCl treated surfaces and analyzed by X-ray photoelectron spectroscopy. Further Ge surface passivation was investigated by thiolation using alkane monothiols and dithiols. The organic passivation layers show good stability with no oxide regrowth observed after 3 days of ambient exposure.

Luminescent gold and silver complexes with the monophosphane 1-(PPh2)-2-Me-C2B10H10 and their conversion to gold micro- and superstructured materials.

Gold and silver complexes containing the monophosphane 1-PPh2-2-Me-l,2-C2B10H10 with different coordination numbers (2, 3) have been synthesized: [M(7,8-(PPh2)2-C2B9H10)(1-PPh2-2-Me-C2B10H10)] (M = Ag, Au) and [Au2(µ-1,n-C2B10H10)(1-PPh2-2-Me-C2B10H10)2] (n = 2, 12). Solid-state pyrolysis of [AuCl(1-PPh2-2-Me-C2B10H10)] and [Au2(µ-1,12-C2B10H10)(1-PPh2-2-Me-C2B10H10)2] in air and of solutions of [AuCl(1-PPh2-2-Me-C2B10H10)] deposited on silicon and silica at 800 °C results in single-crystal Au, confirmed by diffraction and SEM-EDS. The morphology of the pyrolytic products depends on the thermolytic conditions, and different novel 3-D superstructures or microcrystals are possible. We also propose a mechanism for the thermal conversion of these precursors to structural crystalline and phase pure materials. The presence of the carborane monophosphane seems to originate quenching of the luminescence at room temperature in the complexes [Au2(µ-1,n-C2B10H10)(1-PPh2-2-Me-C2B10H10)2], in comparison with other [Au2(µ-1,n-C2B10H10)L2] species (L = monophosphane).

Pore size modulation in electrochemically etched macroporous p-type silicon monitored by FFT impedance spectroscopy and Raman scattering.

The understanding of the mechanisms of macropore formation in p-type Si with respect to modulation of the pore diameter is still in its infancy. In the present work, macropores with significantly modulated diameters have been produced electrochemically in p-type Si. The effect of the current density and the amount of surfactant in the etching solution are shown to influence the modulation in pore diameter and morphology. Data obtained during the etching process by in situ FFT impedance spectroscopy correlate the pore diameter variation with certain time constants found in the kinetics of the dissolution process. Raman scattering and electron microscopy confirm the mesoscopic structure and roughening of the pore walls. Spectroscopic and microscopic methods confirm that the pore wall morphology is correlated with the conditions of pore modulation.

Key scientific challenges in current rechargeable non-aqueous Li-O2 batteries: experiment and theory.

Rechargeable Li-air (henceforth referred to as Li-O2) batteries provide theoretical capacities that are ten times higher than that of current Li-ion batteries, which could enable the driving range of an electric vehicle to be comparable to that of gasoline vehicles. These high energy densities in Li-O2 batteries result from the atypical battery architecture which consists of an air (O2) cathode and a pure lithium metal anode. However, hurdles to their widespread use abound with issues at the cathode (relating to electrocatalysis and cathode decomposition), lithium metal anode (high reactivity towards moisture) and due to electrolyte decomposition. This review focuses on the key scientific challenges in the development of rechargeable non-aqueous Li-O2 batteries from both experimental and theoretical findings. This dual approach allows insight into future research directions to be provided and highlights the importance of combining theoretical and experimental approaches in the optimization of Li-O2 battery systems.

The origin of shape sensitivity in palladium-catalyzed Suzuki-Miyaura cross coupling reactions.

The shape sensitivity of Pd catalysts in Suzuki-Miyaura coupling reactions is studied using nanocrystals enclosed by well-defined surface facets. The catalytic performance of Pd nanocrystals with cubic, cuboctahedral and octahedral morphologies are compared. Superior catalytic reactivity is observed for Pd NCs with {100} surface facets compared to {111} facets. The origin of the enhanced reactivity associated with a cubic morphology is related to the leaching susceptibility of the nanocrystals. Molecular oxygen plays a key role in facilitating the leaching of Pd atoms from the surface of the nanocrystals. The interaction of O2 with Pd is itself facet-dependent, which in turn gives rise to more efficient leaching from {100} facets, compared to {111} facets under the reaction conditions.

Palladium-catalyzed coupling reactions for the functionalization of Si surfaces: superior stability of alkenyl monolayers.

Palladium-catalyzed Suzuki, Heck, and Sonogashira coupling reactions were studied as reaction protocols for organic modification of Si surfaces. These synthetically useful protocols allow for surface modification of alkene, alkyne, and halide terminated surfaces. Surface oxidation and metal contamination were assessed by X-ray photoelectron spectroscopy. The nature of the primary passivation layer was an important factor in the oxidation resistance of the Si surface during the secondary functionalization. Specifically, the use of alkynes as the primary functionalization layer gave superior stability compared to alkene analogues. The ability to utilize Pd-catalyzed coupling chemistries on Si surfaces opens great versatility for potential molecular and nanoscale electronics and sensing/biosensing applications.

Effect of Au nanoparticle spatial distribution on the stability of thin polymer films.

The stability of thin poly(methyl-methacrylate) (PMMA) films of low molecular weight on a solid substrate is controlled by the areal coverage of gold nanoparticles (NPs) present at the air-polymer interface. As the polymer becomes liquid the Au NPs are free to diffuse, coalesce, and aggregate while the polymer film can change its morphology through viscous flow. These processes lead at the same time to the formation of a fractal network of Au NPs and to the development of spinodal instabilities of the free surface of the polymer films. For thinner films a single wavelength is observed, while for thicker films two wavelengths compete. With continued heating the aggregation process results in a decrease in coverage, the networks evolve into disordered particle assemblies, while the polymer films flatten again. The disordering occurs first on the smallest scales and coincides (in thicker films) with the disappearance of the smaller wavelength. The subsequent disordering on larger scales causes the films to flatten.

Propagation of nanopores during anodic etching of n-InP in KOH.

We propose a three-step model of electrochemical nanopore formation in n-InP in KOH that explains how crystallographically oriented etching can occur even though the rate-determining process (hole generation) occurs only at pore tips. The model shows that competition in kinetics between hole diffusion and electrochemical reaction determines the average diffusion distance of holes along the semiconductor surface and this, in turn, determines whether etching is crystallographic. If the kinetics of reaction are slow relative to diffusion, etching can occur at preferred crystallographic sites within a zone in the vicinity of the pore tip, leading to pore propagation in preferential directions. Symmetrical etching of three {111}A faces forming the pore tip causes it to propagate in the (remaining) [111]A direction. As a pore etches, propagating atomic ledges can meet to form sites that can become new pore tips and this enables branching of pores along any of the [111]A directions. The model explains the observed uniform width of pores and its variation with temperature, carrier concentration and electrolyte concentration. It also explains pore wall thickness, and deviations of pore propagation from the [111]A directions. We believe that the model is generally applicable to electrochemical pore formation in III-V semiconductors.

Layered graphitic carbon host formation during liquid-free solid state growth of metal pyrophosphates.

We report a successful ligand- and liquid-free solid state route to form metal pyrophosphates within a layered graphitic carbon matrix through a single step approach involving pyrolysis of previously synthesized organometallic derivatives of a cyclotriphosphazene. In this case, we show how single crystal Mn(2)P(2)O(7) can be formed on either the micro- or the nanoscale in the complete absence of solvents or solutions by an efficient combustion process using rationally designed macromolecular trimer precursors, and present evidence and a mechanism for layered graphite host formation. Using in situ Raman spectroscopy, infrared spectroscopy, X-ray diffraction, high resolution electron microscopy, thermogravimetric and differential scanning calorimetric analysis, and near-edge X-ray absorption fine structure examination, we monitor the formation process of a layered, graphitic carbon in the matrix. The identification of thermally and electrically conductive graphitic carbon host formation is important for the further development of this general ligand-free synthetic approach for inorganic nanocrystal growth in the solid state, and can be extended to form a range of transition metals pyrophosphates. For important energy storage applications, the method gives the ability to form oxide and (pyro)phosphates within a conductive, intercalation possible, graphitic carbon as host-guest composites directly on substrates for high rate Li-ion battery and emerging alternative positive electrode materials.

Metallophosphazene precursor routes to the solid-state deposition of metallic and dielectric microstructures and nanostructures on Si and SiO2.

We present a method for the preparation and deposition of metallic microstructures and nanostructures deposited on silicon and silica surfaces by pyrolysis in air at 800 degrees C of the corresponding metallophosphazene (cyclic or polymer). Atomic force microscopy studies reveal that the morphology is dependent on the polymeric or oligomeric nature of the phosphazene precursor, on the preparation method used, and on the silicon substrate surface (crystalline or amorphous) and its prior inductively couple plasma etching treatment. Microscale and nanoscale structures and high-surface-area thin films of gold, palladium, silver, and tin were successfully deposited from their respective newly synthesized precursors. The characteristic morphology of the deposited nanostructures resulted in varied roughness and increased surface area and was observed to be dependent on the precursor and the metal center. In contrast to island formation from noble metal precursors, we also report a coral of SnP(2)O(7) growth on Si and SiO(2) surfaces from the respective Sn polymer precursor, leaving a self-affine fractal structure with a well-defined roughness exponent that appears to be independent (within experimental error) of the average size of the islands. The nature of the precursor will be shown to influence the degree of surface features, and the mechanism of their formation is presented. The method reported here constitutes a new route to the deposition of single-crystal metallic, oxidic, and phosphate nanostructures and thin films on technologically relevant substrates.

Evolution of 3D Printing Methods and Materials for Electrochemical Energy Storage.

Additive manufacturing has revolutionized the building of materials, and 3D-printing has become a useful tool for complex electrode assembly for batteries and supercapacitors. The field initially grew from extrusion-based methods and quickly evolved to photopolymerization printing, while supercapacitor technologies less sensitive to solvents more often involved material jetting processes. The need to develop higher-resolution multimaterial printers is borne out in the performance data of recent 3D printed electrochemical energy storage devices. Underpinning every part of a 3D-printable battery are the printing method and the feed material. These influence material purity, printing fidelity, accuracy, complexity, and the ability to form conductive, ceramic, or solvent-stable materials. The future of 3D-printable batteries and electrochemical energy storage devices is reliant on materials and printing methods that are co-operatively informed by device design. Herein, the material and method requirements in 3D-printable batteries and supercapacitors are addressed and requirements for the future of the field are outlined by linking existing performance limitations to requirements for printable energy-storage materials, casings, and direct printing of electrodes and electrolytes. A guide to materials and printing method choice best suited for alternative-form-factor energy-storage devices to be designed and integrated into the devices they power is thus provided.

NiF2 Nanorod Arrays for Supercapattery Applications.

A electrode for energy storage cells is possible directly on Ni foam, using a simple reduction process to form NiF2 nanorod arrays (NA). We demonstrate NiF2@Ni NA for a symmetric electrochemical supercapattery electrode. With an areal specific capacitance of 51 F cm-2 at 0.25 mA cm-2 current density and 94% cycling stability, a NiF2@Ni electrode can exhibit supercapattery behavior, a combination of supercapacitor and battery-like redox. The symmetric electrochemical supercapattery delivers 31 W h m-2 energy density and 797 W m-2 power density with 83% retention in a 1 M KOH electrolyte, constituting a step toward manufacturing a laboratory-scale energy storage device based on metal halides. Producing self-grown hierarchically porous nanostructured electrodes on three-dimensional metal foams by displacement reactions may be useful for other metal halides as electrodes for supercapacitors, supercapatteries, and lithium-ion batteries.