Raymond R. Unocic

Dopamine as a Carbon Source: The Controlled Synthesis of Hollow Carbon Spheres and Yolk‐Structured Carbon Nanocomposites

A facile and versatile synthesis using dopamine as a carbon source gives hollow carbon spheres and yolk-shell Au{at}Carbon nanocomposites. The uniform nature of dopamine coatings and their high carbon yield endow the products with high structural integrity. The Au{at}C nanocomposites are catalytically active.

Water desalination using nanoporous single-layer graphene

By creating nanoscale pores in a layer of graphene, it could be used as an effective separation membrane due to its chemical and mechanical stability, its flexibility and, most importantly, its one-atom thickness. Theoretical studies have indicated that the performance of such membranes should be superior to state-of-the-art polymer-based filtration membranes, and experimental studies have recently begun to explore their potential. Here, we show that single-layer porous graphene can be used as a desalination membrane. Nanometre-sized pores are created in a graphene monolayer using an oxygen plasma etching process, which allows the size of the pores to be tuned. The resulting membranes exhibit a salt rejection rate of nearly 100% and rapid water transport. In particular, water fluxes of up to 10(6) g m(-2) s(-1) at 40 °C were measured using pressure difference as a driving force, while water fluxes measured using osmotic pressure as a driving force did not exceed 70 g m(-2) s(-1) atm(-1).

Mesoporous TiO2–B Microspheres with Superior Rate Performance for Lithium Ion Batteries

Advanced energy storage systems such as lithium ion batteries are important approaches to mitigate energy shortage and global climate warming issues that the world is currently facing. High power and high energy density are essential to batteries for applications in electric vehicles, stationary energy storage systems for solar and wind energy as well as smart grids. Because conventional lithium ion batteries are inadequate to meet these needs, advanced materials with high capacity and fast chargedischarge capability are critical for next generation lithium ion batteries. [ 1 ] Titanium dioxide (TiO 2 ) with various polymorphs (anatase, rutile, and TiO 2 –B (bronze)) have been widely investigated as lithium ion battery anode materials, due to their advantages in terms of cost, safety and rate capability. [ 2 ] In particular, the polymorph of TiO 2 –B shows a favorable channel structure for lithium mobility, which results in fast chargedischarge capability of a lithium cell. [ 3 ] It has been identifi ed that the lithium intercalation in TiO 2 –B features a pseudocapacitive process, rather than the solid-state diffusion process observed for anatase and rutile. [ 4 ] Theoretical studies have uncovered that this pseudocapacitive behavior originates from the unique sites and energetics of lithium absorption and diffusion in TiO 2 –B structure. [ 5 ] As a result, TiO 2 –B nanoparticles, [ 6 ] nanotubes, [ 7 ]

Direct exfoliation of natural graphite into micrometre size few layers graphene sheets using ionic liquids

Stable high-concentration suspensions (up to 0.95 mg mL(-1)) of non-oxidized few layer graphene (FLG), five or less sheets, with micrometre-long edges were obtained via direct exfoliation of natural graphite flakes in ionic liquids, such as 1-butyl-3-methyl-imidazolium bis(trifluoro-methane-sulfonyl)imide ([Bmim]-[Tf(2)N]), by tip ultrasonication.

Demonstration of an electrochemical liquid cell for operando transmission electron microscopy observation of the lithiation/delithiation behavior of Si nanowire battery anodes.

Over the past few years, in situ transmission electron microscopy (TEM) studies of lithium ion batteries using an open-cell configuration have helped us to gain fundamental insights into the structural and chemical evolution of the electrode materials in real time. In the standard open-cell configuration, the electrolyte is either solid lithium oxide or an ionic liquid, which is point-contacted with the electrode. This cell design is inherently different from a real battery, where liquid electrolyte forms conformal contact with electrode materials. The knowledge learnt from open cells can deviate significantly from the real battery, calling for operando TEM technique with conformal liquid electrolyte contact. In this paper, we developed an operando TEM electrochemical liquid cell to meet this need, providing the configuration of a real battery and in a relevant liquid electrolyte. To demonstrate this novel technique, we studied the lithiation/delithiation behavior of single Si nanowires. Some of lithiation/delithation behaviors of Si obtained using the liquid cell are consistent with the results from the open-cell studies. However, we also discovered new insights different from the open cell configuration-the dynamics of the electrolyte and, potentially, a future quantitative characterization of the solid electrolyte interphase layer formation and structural and chemical evolution.

Control and elimination of nucleation-related defects in GaP/Si(001) heteroepitaxy

GaP films were grown on offcut Si(001) substrates using migration enhanced epitaxy nucleation followed by molecular beam epitaxy, with the intent of controlling and eliminating the formation of heterovalent (III-V/IV) nucleation-related defects—antiphase domains, stacking faults, and microtwins. Analysis of these films via reflection high-energy electron diffraction, atomic force microscopy, and both cross-sectional and plan-view transmission electron microscopies indicate high-quality GaP layers on Si that portend a virtual GaP substrate technology, in which the aforementioned extended defects are simultaneously eliminated. The only prevalent remaining defects are the expected misfit dislocations due to the GaP–Si lattice mismatch.

Characterization of Metamorphic GaAsP/Si Materials and Devices for Photovoltaic Applications

GaAsyP1-y anion-sublattice compositionally graded buffers and device structures were grown directly on Si(100) substrates by way of a high-quality GaP integration layer, yielding GaAsP target layers having band gaps of photovoltaic interest (1.65-1.8 eV), free of antiphase domains/borders, stacking faults, and microtwins. GaAsyP1-y growths on both Si and GaP substrates were compared via high-resolution X-ray diffractometry of the metamorphic buffers and deep-level transient spectroscopy (DLTS) of p+-n diodes that are lattice matched to the final buffer layer. Structural analysis indicates highly efficient epitaxial relaxation throughout the entire growth structure for both types of samples and suggests no significant difference in physical behavior between the two types of samples. DLTS measurements performed on GaAsP diodes fabricated on both Si and GaP substrates reveal the existence of identical sets of traps residing in the n-type GaAsP layers in both types of samples: a single majority carrier (electron) trap, which is located at EC - 0.18 eV, and a single minority carrier (hole) trap, which is located at EV + 0.71 eV. Prototype 1.75-eV GaAsP solar cell test devices grown on GaAsyP1-y/Si buffers show good preliminary performance characteristics and offer great promise for future high-efficiency III-V photovoltaics integrated with Si substrates and devices.

Nanoscale Imaging of Fundamental Li Battery Chemistry: Solid-Electrolyte Interphase Formation and Preferential Growth of Lithium Metal Nanoclusters

The performance characteristics of Li-ion batteries are intrinsically linked to evolving nanoscale interfacial electrochemical reactions. To probe the mechanisms of solid electrolyte interphase (SEI) formation and to track Li nucleation and growth mechanisms from a standard organic battery electrolyte (LiPF6 in EC:DMC), we used in situ electrochemical scanning transmission electron microscopy (ec-S/TEM) to perform controlled electrochemical potential sweep measurements while simultaneously imaging site-specific structures resulting from electrochemical reactions. A combined quantitative electrochemical measurement and STEM imaging approach is used to demonstrate that chemically sensitive annular dark field STEM imaging can be used to estimate the density of the evolving SEI and to identify Li-containing phases formed in the liquid cell. We report that the SEI is approximately twice as dense as the electrolyte as determined from imaging and electron scattering theory. We also observe site-specific locations where Li nucleates and grows on the surface and edge of the glassy carbon electrode. Lastly, this report demonstrates the investigative power of quantitative nanoscale imaging combined with electrochemical measurements for studying fluid-solid interfaces and their evolving chemistries.

Aqueous proton transfer across single-layer graphene

Proton transfer across single-layer graphene proceeds with large computed energy barriers and is therefore thought to be unfavourable at room temperature unless nanoscale holes or dopants are introduced, or a potential bias is applied. Here we subject single-layer graphene supported on fused silica to cycles of high and low pH, and show that protons transfer reversibly from the aqueous phase through the graphene to the other side where they undergo acid–base chemistry with the silica hydroxyl groups. After ruling out diffusion through macroscopic pinholes, the protons are found to transfer through rare, naturally occurring atomic defects. Computer simulations reveal low energy barriers of 0.61–0.75 eV for aqueous proton transfer across hydroxyl-terminated atomic defects that participate in a Grotthuss-type relay, while pyrylium-like ether terminations shut down proton exchange. Unfavourable energy barriers to helium and hydrogen transfer indicate the process is selective for aqueous protons.

Direct Visualization of Dendrite Nucleation and Growth Kinetics during Lithium Deposition with in situ Electrochemical Transmission Electron Microscopy

Deposition of Li is a major safety concern existing in Li-ion secondary batteries. Here we perform the first in situ high spatial resolution measurement coupled with real-time quantitative electrochemistry to characterize SEI formation on gold using a standard battery electrolyte. We demonstrate that a dendritic SEI forms prior to Li deposition and that it remains on the surface after Li electrodissolution.