Electrochemically-Formed Disordered Rock Salt ω-Li VMoO as a Fast-Charging Li-Ion Electrode Material.

Electrochemically-formed disordered rock salt compounds are an emerging class of Li-ion electrode materials for fast-charging energy storage. However, the specific factors that govern the formation process and the resulting charge storage performance are not well understood. Here, we characterize the transformation mechanism and charge storage properties of an electrochemically-formed disordered rock salt from VMoO (VMO).

Using Bulky Dodecaborane-Based Dopants to Produce Mobile Charge Carriers in Amorphous Semiconducting Polymers.

Conjugated polymers are a versatile class of electronic materials featured in a variety of next-generation electronic devices. The utility of such polymers is contingent in large part on their electrical conductivity, which depends both on the density of charge carriers (polarons) and on the carrier mobility. Carrier mobility, in turn, is largely controlled by the separation between the polarons and dopant counterions, as counterions can produce Coulombic traps.

Measuring Heat Dissipation and Entropic Potential in Battery Cathodes Made with Conjugated and Conventional Polymer Binders Using Calorimetry.

This study explores the influence of electronic and ionic conductivities on the behavior of conjugated polymer binders through the measurement of entropic potential and heat generation in an operating lithium-ion battery. Specifically, the traditional poly(vinylidene fluoride) (PVDF) binder in LiNiCoAlO (NCA) cathode electrodes was replaced with semiconducting polymer binders based on poly(3,4-propylenedioxythiophene). Two conjugated polymers were explored: one is a homopolymer with all aliphatic side chains, and the other is a copolymer with both aliphatic and ethylene oxide side chains.

High-pressure studies of size dependent yield strength in rhenium diboride nanocrystals.

The superhard ReB system is the hardest pure phase diboride synthesized to date. Previously, we have demonstrated the synthesis of nano-ReB and the use of this nanostructured material for texture analysis using high-pressure radial diffraction. Here, we investigate the size dependence of hardness in the nano-ReB system using nanocrystalline ReB with a range of grain sizes (20-60 nm).

Establishing reaction networks in the 16-electron sulfur reduction reaction.

The sulfur reduction reaction (SRR) plays a central role in high-capacity lithium sulfur (Li-S) batteries. The SRR involves an intricate, 16-electron conversion process featuring multiple lithium polysulfide intermediates and reaction branches. Establishing the complex reaction network is essential for rational tailoring of the SRR for improved Li-S batteries, but represents a daunting challenge.

Understanding How the Suppression of Insertion-Induced Phase Transitions Leads to Fast Charging in Nanoscale LiMoO.

Fast-charging Li-ion batteries are technologically important for the electrification of transportation and the implementation of grid-scale storage, and additional fundamental understanding of high-rate insertion reactions is necessary to overcome current rate limitations. In particular, phase transformations during ion insertion have been hypothesized to slow charging. Nanoscale materials with modified transformation behavior often show much faster kinetics, but the mechanism for these changes and their specific contribution to fast-charging remain poorly understood.

Vertex Differentiation Strategy for Tuning the Physical Properties of -Dodecaborate Weakly Coordinating Anions.

We report the synthesis and characterization of various compounds containing the 1,7,9-hydroxylated -dodecahydrododecaborate (BH(OH)) cluster motif. Specifically, we show how the parent compound can be synthesized on the multigram scale and further perhalogenated, leading to a new class of vertex-differentiated weakly coordinating anions. We show that a postmodification of the hydroxyl groups by alkylation affords further opportunities for tailoring these anions' stability, steric bulk, and solubility properties.

Measurement of Magnetoelectric Coupling and Strain Transfer in Multiferroic Nanocomposites of CoFeO and HfZrO with Residual Porosity.

With increasing applications for voltage-controlled magnetism, the need to more fully understand magnetoelectric coupling and strain transfer in nanostructured multiferroic composites has also increased. Here, multiferroic nanocomposites were synthesized using block copolymer templating to create mesoporous cobalt ferrite (CFO), followed by partly filling the pores with ferroelectric zirconium-substituted hafnia (HZO) using atomic layer deposition (ALD) to produce a porous multiferroic composite with enhanced mechanical flexibility. Upon electrical poling of the nanocomposite, we observed large changes in the magnetization.

A direct and clean route to MXenes.

New, scalable methods synthesize two-dimensional carbide and nitride materials.

Using small angle x-ray scattering to examine the aggregation mechanism in silica nanoparticle-based ambigels for improved optical clarity.

Silica-based aerogels are a promising low-cost solution for improving the insulation efficiency of single-pane windows and reducing the energy consumption required for space heating and cooling. Two key material properties required are high porosity and small pore sizes, which lead to low thermal conductivity and high optical transparency, respectively. However, porosity and pore size are generally directly linked, where high porosity materials also have large pore sizes.

Molecular Dynamics Study of the Thermodynamics of Integer Charge Transfer vs Charge-Transfer Complex Formation in Doped Conjugated Polymers.

Molecular dopants such as 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (FTCNQ) can interact with conjugated polymers such as poly(3-hexylthiophene-2,5-diyl) (P3HT) in two different ways: they can undergo integer charge transfer (ICT) or they can form a partial-charge-transfer complex (CTC). Both are seen experimentally, but the CTC has been challenging to characterize, making it difficult to answer questions such as the following. Which polymorph is more stable? Do they have similar barriers for formation? Is there a thermodynamic route to convert one to the other? Here, we study the structure and the thermodynamics of bulk FTCNQ-doped P3HT with all-atom molecular dynamics simulations, using thermodynamic integration to calculate the relative free energies.

Tuning Exchange Coupling in a New Family of Nanocrystal-Based Granular Multiferroics Using an Applied Electric Field.

In this work, we demonstrate an experimental realization of a granular multiferroic composite, where the magnetic state of a nanocrystal array is modified by tuning the interparticle exchange coupling using an applied electric field. Previous theoretical models of a granular multiferroic composite predicted a unique magnetoelectric coupling mechanism, in which the magnetic spins of the ensemble are governed by interparticle exchange. The extent of these exchange interactions can be controlled by varying the local dielectric environment between grains.

Transparent silica aerogel slabs synthesized from nanoparticle colloidal suspensions at near ambient conditions on omniphobic liquid substrates.

This paper presents a novel sol-gel method to synthesize large and thick silica aerogel monoliths at near ambient conditions using a commercial aqueous solution of colloidal silica nanoparticles as building blocks. To achieve slabs with high visible transmittance and low thermal conductivity, the method combines the strategies of (i) synthesizing gels on an omniphobic perfluorocarbon liquid substrate, (ii) aging at temperatures above room temperature, and (iii) performing solvent exchange with a low-surface-tension organic solvent prior to ambient drying. The omniphobic liquid substrates were used to prevent cracking and ensure an optically-smooth surface, while nanoparticle building blocks were small (<10 nm) to limit volumetric light scattering.

Seeded-Growth Experiment Demonstrating Size- and Shape-Dependence on Gold Nanoparticle-Light Interactions.

Gold nanoparticles are exciting materials in nanotechnology and nanoscience research and are being applied across a wide range of fields including imaging, chemical sensing, energy storage, and cancer therapies. In this experiment, students will synthesize two sizes of gold nanospheres (~20 nm and ~100 nm) and will create gold nanostars utilizing a seed-mediated growth synthetic approach. Students will compare how each sample interacts differently with light (absorption and scattering) based on the nanoparticles' size and shape.

Understanding Stabilization in Nanoporous Intermetallic Alloy Anodes for Li-Ion Batteries Using Transmission X-ray Microscopy.

Tin-based alloying anodes are exciting due to their high energy density. Unfortunately, these materials pulverize after repetitive cycling due to the large volume expansion during lithiation and delithiation; both nanostructuring and intermetallic formation can help alleviate this structural damage. Here, these ideas are combined in nanoporous antimony-tin (NP-SbSn) powders, synthesized by a simple and scalable selective-etching method.

A partnership to build scientific capacity of Rwanda's future conservationists: The Memoirs Program.

The future of primates depends on conservationists in primate range countries having the education and opportunities needed to facilitate conservation efforts. However, most primates are found in countries where conservation is underfunded. Rwanda is home to 14 primate species, with three being listed as endangered on the International Union for Conservation of Nature (IUCN) Red List.

Fjord-Edge Graphene Nanoribbons with Site-Specific Nitrogen Substitution.

The synthesis of graphene nanoribbons (GNRs) that contain site-specifically substituted backbone heteroatoms is one of the essential goals that must be achieved in order to control the electronic properties of these next generation organic materials. We have exploited our recently reported solid-state topochemical polymerization/cyclization-aromatization strategy to convert the simple 1,4-bis(3-pyridyl)butadiynes into the fjord-edge nitrogen-doped graphene nanoribbon structures (fjord-edge N[8]GNRs). Structural assignments are confirmed by CP/MAS C NMR, Raman, and XPS spectroscopy.

Tunable Dopants with Intrinsic Counterion Separation Reveal the Effects of Electron Affinity on Dopant Intercalation and Free Carrier Production in Sequentially Doped Conjugated Polymer Films.

Carrier mobility in doped conjugated polymers is limited by Coulomb interactions with dopant counterions. This complicates studying the effect of the dopant's oxidation potential on carrier generation because different dopants have different Coulomb interactions with polarons on the polymer backbone. Here, dodecaborane (DDB)-based dopants are used, which electrostatically shield counterions from carriers and have tunable redox potentials at constant size and shape.

Fast-Charging Cathodes from Polymer-Templated Mesoporous LiVPOF.

Fast-charging cathodes with high operating voltages are critical to the development of high energy and power density lithium-ion batteries. One route to fast-charging battery materials is through the formation of nanoporous networks, but these methods are often limited by the high calcination temperatures required for synthesis. Here, we report the synthesis of carbon-coated nanoporous LiVPOF with excellent rate capabilities that can be stably cycled up to 4.

Controlling Thermal Conductivity in Mesoporous Silica Films Using Pore Size and Nanoscale Architecture.

This work investigates the effect of wall thickness on the thermal conductivity of mesoporous silica materials made from different precursors. Sol-gel- and nanoparticle-based mesoporous silica films were synthesized by evaporation-induced self-assembly using either tetraethyl orthosilicate or premade silica nanoparticles. Since wall thickness and pore size are correlated, a variety of polymer templates were used to achieve pore sizes ranging from 3-23 nm for sol-gel-based materials and 10-70 nm for nanoparticle-based materials.

Dopant-Induced Ordering of Amorphous Regions in Regiorandom P3HT.

Despite the fact that molecular doping of semiconducting polymers has emerged as a valuable strategy for improving the performance of organic electronic devices, the fundamental dopant-polymer interactions are not fully understood. Here we use 2-D grazing incidence wide-angle X-ray scattering (GIWAXS) to demonstrate that adding oxidizing small-molecule dopants, such as 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (FTCNQ) and FeCl, into the amorphous conjugated polymer, regiorandom poly(3-hexylthiophene-2,5-diyl) (RRa-P3HT), improves polymer ordering and induces a change in domain orientation from isotropic to mostly edge-on. Doping thus causes RRa-P3HT to behave similarly to the more ordered regioregular P3HT.

Synthesis and High-Pressure Mechanical Properties of Superhard Rhenium/Tungsten Diboride Nanocrystals.

Rhenium diboride is an established superhard compound that can scratch diamond and can be readily synthesized under ambient pressure. Here, we demonstrate two synergistic ways to further enhance the already high yield strength of ReB. The first approach builds on previous reports where tungsten is doped into ReB at concentrations up to 48 at.

Poly(3-alkylthiophene)- block-poly(3-alkylselenophene)s: Conjugated Diblock Co-polymers with Atypical Self-Assembly Behavior.

Understanding self-assembly behavior and resulting morphologies in block co-polymer films is an essential aspect of chemistry and materials science. Although the self-assembly of amorphous coil-coil block co-polymers is relatively well understood, that of semicrystalline block co-polymers where each block has distinct crystallization properties remains unclear. Here, we report a detailed study to elucidate the rich self-assembly behavior of conjugated thiophene-selenophene (P3AT- b-P3AS) block co-polymers.