The Bonding Nature and Adhesion of Polyacrylic Acid Coating on Li-Metal for Li Dendrite Prevention.

The success of polyacrylic acid (PAA) to suppress Li dendrite growth suggests that the mechanical properties of polymer-based coatings, including the modulus, toughness, and interfacial adhesion are important design criteria. However, the measurement of the adhesion of thin PAA, as well as other polymer coatings to the reactive Li-metal anode surface is limited experimentally and challenging computationally. In this paper, a strategy was proposed to estimate the adhesion and delamination of the PAA(polymer)/Li interface, based on the bonding nature at the simpler PAA (oligomer)/Li interfaces using density functional theory calculations. It has been shown that the carboxylic acid groups in PAA reacted strongly with metallic Li, which significantly enhances the interfacial adhesion through the Li-O bonds formation, Li ionization and its incorporation into PAA, and -H or -OH termination of Li after decomposition of the COOH functional group. During delamination, it was found that the most likely PAA delamination route involved breaking partial Li-O bonds and lifting some ionized Li atoms from the Li-metal, especially for the Li atoms that showed a charge closer to +1 or are bonded with two O atoms from PAA. Based on the average bonding energies from PAA(oligomer)/Li interface delamination calculations, the work of separation, Wsep, of the PAA(polymer)/Li interface was estimated to be ∼1.0 (J/m2). The high Wsep of PAA (polymer)/Li was comparable with the Li2O/Li interface and higher than Li2CO3/Li and LiF/Li interfaces. This order correlated well with the areal density of Li-O bonds, which can serve as a descriptor for the interfacial adhesion. This computational approach can be applied to other interfaces with polymer-based coatings.

Hierarchical porous silicon structures with extraordinary mechanical strength as high-performance lithium-ion battery anodes.

Porous structured silicon has been regarded as a promising candidate to overcome pulverization of silicon-based anodes. However, poor mechanical strength of these porous particles has limited their volumetric energy density towards practical applications. Here we design and synthesize hierarchical carbon-nanotube@silicon@carbon microspheres with both high porosity and extraordinary mechanical strength (>200 MPa) and a low apparent particle expansion of ~40% upon full lithiation. The composite electrodes of carbon-nanotube@silicon@carbon-graphite with a practical loading (3 mAh cm-2) deliver ~750 mAh g-1 specific capacity, <20% initial swelling at 100% state-of-charge, and ~92% capacity retention over 500 cycles. Calendered electrodes achieve ~980 mAh cm-3 volumetric capacity density and <50% end-of-life swell after 120 cycles. Full cells with LiNi1/3Mn1/3Co1/3O2 cathodes demonstrate >92% capacity retention over 500 cycles. This work is a leap in silicon anode development and provides insights into the design of electrode materials for other batteries.

Reinforced Composite Film on Lithium Metal Electrodes through Aryl Chlorosilane Treatment.

Lithium metal has great potential to become the anode for the next generation of high-energy-density batteries because of high capacity (3860 mAh g-1), lowest negative electrochemical potential, and low density. Low cycle efficiency and dendrite growth are two critical barriers for rechargeable batteries using Li metal as the anode, mainly due to the coupled mechanical/chemical degradation of the solid electrolyte interphase (SEI) layer formed on the Li metal surface. In this work, we found that a composite film of lithium aryl silanolate with uniformly distributed submicron LiCl-dominant particles can in situ form on the Li metal surface by treating Li with a single phenyl substituted chlorosilane. The synergistic effect of the high modulus of the composite film resulted from both well-dispersed LiCl particles and phenyl ring structures, and the extra reinforcement by the π-π interaction of aryl silanolate molecules that coated on LiCl particles and Li electrode surface endows the artificial surface coating film with high modulus and stability, and, thus, suitable as an artificial SEI layer. The coin cells using the lithium metal electrodes with this Lithium silanolate/LiCl particle composite coating layer showed an improved cycle efficiency and the extended life in a relatively harsh cycling condition.

Pressure compression of CdSe nanoparticles into luminescent nanowires.

Oriented attachment (OA) of synthetic nanocrystals is emerging as an effective means of fabricating low-dimensional nanoscale materials. However, OA relies on energetically favorable nanocrystal facets to grow nanostructured materials. Consequently, nanostructures synthesized through OA are generally limited to a specific crystal facet in their final morphology. We report our discovery that high-pressure compression can induce consolidation of spherical CdSe nanocrystal arrays, leading to unexpected one-dimensional semiconductor nanowires that do not exhibit the typical crystal facet. In particular, in situ high-pressure synchrotron x-ray scattering, optical spectroscopy, and high-resolution transmission electron microscopy characterizations indicate that by manipulating the coupling between nanocrystals through external pressure, a reversible change in nanocrystal assemblies and properties can be achieved at modest pressure. When pressure is increased above a threshold, these nanocrystals begin to contact one another and consolidate, irreversibly forming one-dimensional luminescent nanowires. High-fidelity molecular dynamics (MD) methods were used to calculate surface energies and simulate compression and coalescence mechanisms of CdSe nanocrystals. The MD results provide new insight into nanowire assembly dynamics and phase stability of nanocrystalline structures.

Corrigendum: Superfast assembly and synthesis of gold nanostructures using nanosecond low-temperature compression via magnetic pulsed power.

This corrects the article DOI: 10.1038/ncomms14778.

Superfast assembly and synthesis of gold nanostructures using nanosecond low-temperature compression via magnetic pulsed power.

Gold nanostructured materials exhibit important size- and shape-dependent properties that enable a wide variety of applications in photocatalysis, nanoelectronics and phototherapy. Here we show the use of superfast dynamic compression to synthesize extended gold nanostructures, such as nanorods, nanowires and nanosheets, with nanosecond coalescence times. Using a pulsed power generator, we ramp compress spherical gold nanoparticle arrays to pressures of tens of GPa, demonstrating pressure-driven assembly beyond the quasi-static regime of the diamond anvil cell. Our dynamic magnetic ramp compression approach produces smooth, shockless (that is, isentropic) one-dimensional loading with low-temperature states suitable for nanostructure synthesis. Transmission electron microscopy clearly establishes that various gold architectures are formed through compressive mesoscale coalescences of spherical gold nanoparticles, which is further confirmed by in-situ synchrotron X-ray studies and large-scale simulation. This nanofabrication approach applies magnetically driven uniaxial ramp compression to mimic established embossing and imprinting processes, but at ultra-short (nanosecond) timescales.

Pressure-Tuned Structure and Property of Optically Active Nanocrystals.

Investigations through high-pressure X-ray scattering and spectroscopy in combination with theoretical computations shows that high-pressure compression can systematically tune the optical properties and mechanical stability of the molecular nanocrystals.

Atomic layer deposition of L-alanine polypeptide.

L-Alanine polypeptide thin films were synthesized via atomic layer deposition (ALD). Instead of using an amino acid monomer as the precursor, an L-alanine amino acid derivatized with a protecting group was used to prevent self-polymerization, increase the vapor pressure, and allow linear cycle-by-cycle growth emblematic of ALD. The successful deposition of a conformal polypeptide film has been confirmed by FTIR, TEM, and Mass Spectrometry, and the ALD process has been extended to polyvaline.

Oxygen vacancy enhanced photocatalytic activity of pervoskite SrTiO(3).

A facile and general method has been developed to fabricate oxygen vacancies on perovskite SrTiO3 (STO) nanocrystals through a controllable solid-state reaction of NaBH4 and SrTiO3 nanocrystals. STO samples with tunable color, oxygen vacancy concentration on nanocrystal surface have been synthesized. TEM results reveal that these STO samples have a crystalline core/amorphous shell structure (SrTiO3@SrTiO3-x). XPS and EPR results disclose that the oxygen vacancy concentration increases with the increase of reaction time and temperature. The concentration of oxygen vacancies calculated from TGA data, could reach 5.07% (atom) in this study. UV-vis spectra and photocatalytic results indicate that oxygen vacancies on STO surface play an important role in influencing the light absorption and photocatalytic performance. However, an excess amount of oxygen vacancies leads to a decrease of photocatalytic performance. The optimal photocatalytic activity for H2 production under UV-vis irradiation is up to 2.2 mmol h(-1) g(-1), which is about 2.3 times than the original SrTiO3, corresponding to 3.28% (atom) of oxygen vacancy concentration.

Stress-induced phase transformation and optical coupling of silver nanoparticle superlattices into mechanically stable nanowires.

One-dimensional silver materials display unique optical and electrical properties with promise as functional blocks for a new generation of nanoelectronics. To date, synthetic approaches and property engineering of silver nanowires have primarily focused on chemical methods. Here we report a simple physical method of metal nanowire synthesis, based on stress-induced phase transformation and sintering of spherical Ag nanoparticle superlattices. Two phase transformations of nanoparticles under stress have been observed at distinct length scales. First, the lattice dimensions of silver nanoparticle superlattices may be reversibly manipulated between 0-8 GPa compressive stresses to enable systematic and reversible changes in mesoscale optical coupling between silver nanoparticles. Second, stresses greater than 8 GPa induced an atomic lattice phase transformation, which induced sintering of silver nanoparticles into micron-length scale nanowires. The nanowire synthesis mechanism displays a dependence on both nanoparticle crystal surface orientation and presence of particular grain boundaries to enable nanoparticle consolidation into nanowires.

Poly(N-isopropylacrylamide) surfactant-functionalized responsive silver nanoparticles and superlattices.

Metal nanoparticles exhibit unique optical characteristics in visible spectra produced by local surface plasmon resonance (SPR) for a wide range of optical and electronic applications. We report the synthesis of poly(N-isopropylacrylamide) surfactant (PNIPAM-C18)-functionalized metal nanoparticles and ordered superlattice arrays through an interfacial self-assembly process. The method is simple and reliable without using complex chemistry. The PNIPAM-C18-functionalized metal nanoparticles and ordered superlattices exhibit responsive behavior modulated by external temperature and relative humidity (RH). In situ grazing-incidence small-angle X-ray scattering studies confirmed that the superlattice structure of PNIPAM-C18 surfactant-functionalized nanoparticle arrays shrink and spring back reversibly based on external thermal and RH conditions, which allow flexible manipulation of interparticle spacing for tunable SPR. PNIPAM-C18 surfactants play a key role in accomplishing this responsive property. The ease of fabrication of the responsive nanostructure facilitates investigation of nanoparticle coupling that depends on interparticle separation for potential applications in chemical and biological sensors as well as energy storage devices.

Instant gelation synthesis of 3D porous MoS2@C nanocomposites for lithium ion batteries.

Three-dimensional (3D) nanoporous architectures, possessing high surface area, massive pores, and excellent structural stability, are highly desirable for many applications including catalysts and electrode materials in lithium ion batteries. However, the preparation of such materials remains a major challenge. Here, we introduce a novel method, instant gelation, for the synthesis of such materials. The as-prepared porous 3D MoS2@C nanocomposites, with layered MoS2 clusters or strips ingrained in porous and conductive 3D carbon matrix, indeed showed excellent electrochemical performance when applied as anode materials for lithium ion batteries. Its interconnected carbon network ensures good conductivity and fast electron transport; the micro-, and mesoporous nature effectively shortens the lithium ion diffusion path and provides room necessary for volume expansion. The large specific surface area is beneficial for a better contact between electrode materials and electrolyte.

Colloidal graphene quantum dots with well-defined structures.

When the size of a semiconductor crystal is reduced to the nanometer scale, the crystal boundary significantly modifies electron distribution, making properties such as bandgap and energy relaxation dynamics size dependent. This phenomenon, known as quantum confinement, has been demonstrated in many semiconductor materials, leading to practical applications in areas such as bioimaging, photovoltaics, and light-emitting diodes. Graphene, a unique type of semiconductor, is a two-dimensional crystal with a zero bandgap and a zero effective mass of charge carriers. Consequently, we expect new phenomena from nanometer-sized graphene, or graphene quantum dots (QDs), because the energy of charge carriers in graphene follows size-scaling laws that differ from those in other semiconductors. From a chemistry point of view, graphene is made of carbon, an element for which researchers have developed a whole branch of chemistry. Thus, it is possible to synthesize graphene QDs through stepwise, well-controlled organic chemistry, achieving structures with an atomic precision that has not been possible for any other semiconductor materials. Recently, we developed a new solubilizing strategy that led to synthesis of stable colloidal graphene QDs with more than 100 conjugated carbon atoms, allowing us to study their properties in a new size regime. In this Account, we review our recent progress working with the colloidal graphene QDs, including their synthesis and stabilization, tuning of their properties, and new phenomena in energy relaxation dynamics. In particular, we have observed extraordinarily slow "electron cooling"--the relaxation of electrons from high excited states to lower ones. With further investigation, these high-energy electrons could potentially be harvested in solar energy applications, for example, creating more efficient photovoltaic cells. We discuss additional emerging opportunities with these new materials and current challenges, hoping to draw the interest of researchers in various fields to overcome these obstacles.

Alignment of colloidal graphene quantum dots on polar surfaces.

Controlling the orientation of nanostructures with anisotropic shapes is essential for taking advantage of their anisotropic electrical, optical, and transport properties in electro-optical devices. For large-area alignment of nanocrystals, so far orientations are mostly induced and controlled by external physical parameters, such as applied fields or changes in concentration. Herein we report on assemblies of colloidal graphene quantum dots, a new type of disk-shaped nanostructures, on polar surfaces and the control of their orientations. We show that the orientations of the graphene quantum dots can be determined, either in- or out-of-plane with the substrate, by chemical functionalization that introduces orientation-dependent interactions between the quantum dots and the surfaces.

Independent Tuning of the Band Gap and Redox Potential of Graphene Quantum Dots.

The band gap and redox potential of semiconductor nanocrystals are two quantities of primary importance for their applications in energy conversion devices. Herein, we report on covalent functionalization of colloidal graphene quantum dots through a solution-chemistry approach and studies of their band gaps and redox potentials. We show that their band gaps and redox potentials can be independently controlled, the former by size and the latter by functionalization. The size and the functionalization dependence of the properties can be numerically reproduced with tight-binding calculations, which thus provides a simple theoretical tool to guide the design of graphene QDs with desired properties.

Large, solution-processable graphene quantum dots as light absorbers for photovoltaics.

Graphenes have very attractive properties for photovoltaics. Their tunable bandgap and large optical absorptivity are desirable for efficient light harvesting. Their electronic levels and interfacing with other materials for charge transfer processes can both be tuned with well-developed carbon chemistry. Graphenes have also been shown to have very large charge mobilities, which could be useful for charge collection in solar cells. In addition, they consist of elements abundant on Earth and are environmentally friendly. However, these important properties have not been taken advantage of because graphenes that are large enough to be useful for photovoltaics have extremely poor solubility and have a strong tendency to aggregate into graphite. Here we present a novel solubilization strategy for large graphene nanostructures. It has enabled us to synthesize solution-processable, black graphene quantum dots with uniform size through solution chemistry, and we show that they can be used as sensitizers for solar cells.

Synthesis and properties of hyperbranched conjugated porphyrins.

[reaction: see text] Hyperbranched conjugated porphyrin arrays were prepared by one-pot Suzuki polycondensation of AB3 and AB3 + C4 approaches.

Porphyrins with four monodisperse oligofluorene arms as efficient red light-emitting materials.

A family of red light-emitting star-shaped porphyrins with four monodisperse conjugated oligofluorene arms was prepared by using two key reactions: Lindsey condensation and Suzuki-Miyaura cross coupling reactions. All porphyrins exhibit high quantum yields (about 0.22) and good solubility in common organic solvents, and form high-quality solid films. Optical studies showed that the star-shaped oligomers could absorb blue light and emit saturated red light via efficient energy transfer from the fluorene segments to the porphyrin core.