Tuo Wang

High-Performance Hydrogen Evolution from MoS2(1-x) P(x) Solid Solution.

A MoS2(1-x) P(x) solid solution (x = 0 to 1) is formed by thermally annealing mixtures of MoS2 and red phosphorus. The effective and stable electrocatalyst for hydrogen evolution in acidic solution holds promise for replacing scarce and expensive platinum that is used in present catalyst systems. The high performance originates from the increased surface area and roughness of the solid solution.

In Situ Formation of Metal Oxide Nanocrystals Embedded in Laser-Induced Graphene

Hybrid materials incorporating the advantages of graphene and nanoparticles have been widely studied. Here we develop an improved cost-effective approach for preparation of porous graphene embedded with various types of nanoparticles. Direct laser scribing on metal-complex-containing polyimide film leads to in situ formation of nanoparticles embedded in porous graphene. These materials are highly active in electrochemical oxygen reduction reactions, converting O2 into OH(-), with a low metal loading of less than 1 at. %. In addition, the nanoparticles can vary from metal oxide to metal dichalcogenides through lateral doping, making the composite active in other electrocatalytic reactions such as hydrogen evolution.

Three-Dimensional Printed Graphene Foams

An automated metal powder three-dimensional (3D) printing method for in situ synthesis of free-standing 3D graphene foams (GFs) was successfully modeled by manually placing a mixture of Ni and sucrose onto a platform and then using a commercial CO2 laser to convert the Ni/sucrose mixture into 3D GFs. The sucrose acted as the solid carbon source for graphene, and the sintered Ni metal acted as the catalyst and template for graphene growth. This simple and efficient method combines powder metallurgy templating with 3D printing techniques and enables direct in situ 3D printing of GFs with no high-temperature furnace or lengthy growth process required. The 3D printed GFs show high-porosity (∼99.3%), low-density (∼0.015g cm-3), high-quality, and multilayered graphene features. The GFs have an electrical conductivity of ∼8.7 S cm-1, a remarkable storage modulus of ∼11 kPa, and a high damping capacity of ∼0.06. These excellent physical properties of 3D printed GFs indicate potential applications in fields requiring rapid design and manufacturing of 3D carbon materials, for example, energy storage devices, damping materials, and sound absorption.

High Performance Electrocatalytic Reaction of Hydrogen and Oxygen on Ruthenium Nanoclusters

The development of catalytic materials for the hydrogen oxidation, hydrogen evolution, oxygen reduction or oxygen evolution reactions with high reaction rates and low overpotentials are key goals for the development of renewable energy. We report here Ru(0) nanoclusters supported on nitrogen-doped graphene as high-performance multifunctional catalysts for the hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR), showing activities similar to that of commercial Pt/C in alkaline solution. For HER performance in alkaline media, sample Ru/NG-750 reaches 10 mA cm-2 at an overpotential of 8 mV with a Tafel slope of 30 mV dec-1. The high HER performance in alkaline solution is advantageous because most catalysts for ORR and oxygen evolution reaction (OER) also prefer alkaline solution environment whereas degrade in acidic electrolytes. For ORR performance, Ru/NG effectively catalyzes the conversion of O2 into OH- via a 4e process at a current density comparable to that of Pt/C. The unusual catalytic activities of Ru(0) nanoclusters reported here are important discoveries for the advancement of renewable energy conversion reactions.

Composites of Graphene Nanoribbon Stacks and Epoxy for Joule Heating and Deicing of Surfaces

A conductive composite of graphene nanoribbon (GNR) stacks and epoxy is fabricated. The epoxy is filled with the GNR stacks, which serve as a conductive additive. The GNR stacks are on average 30 nm thick, 250 nm wide, and 30 μm long. The GNR-filled epoxy composite exhibits a conductivity >100 S/m at 5 wt % GNR content. This permits application of the GNR-epoxy composite for deicing of surfaces through Joule (voltage-induced) heating generated by the voltage across the composite. A power density of 0.5 W/cm(2) was delivered to remove ∼1 cm-thick (14 g) monolith of ice from a static helicopter rotor blade surface in a -20 °C environment.

Ultrafast Charging High Capacity Asphalt–Lithium Metal Batteries

Li metal has been considered an outstanding candidate for anode materials in Li-ion batteries (LIBs) due to its exceedingly high specific capacity and extremely low electrochemical potential, but addressing the problem of Li dendrite formation has remained a challenge for its practical rechargeable applications. In this work, we used a porous carbon material made from asphalt (Asp), specifically untreated gilsonite, as an inexpensive host material for Li plating. The ultrahigh surface area of >3000 m2/g (by BET, N2) of the porous carbon ensures that Li was deposited on the surface of the Asp particles, as determined by scanning electron microscopy, to form Asp-Li. Graphene nanoribbons (GNRs) were added to enhance the conductivity of the host material at high current densities, to produce Asp-GNR-Li. Asp-GNR-Li has demonstrated remarkable rate performance from 5 A/gLi (1.3C) to 40 A/gLi (10.4C) with Coulombic efficiencies >96%. Stable cycling was achieved for more than 500 cycles at 5 A/gLi, and the areal capacity reached up to 9.4 mAh/cm2 at a highest discharging/charging rate of 20 mA/cm2 that was 10× faster than that of typical LIBs, suggesting use in ultrafast charging systems. Full batteries were also built combining the Asp-GNR-Li anodes with a sulfurized carbon cathode that possessed both high power density (1322 W/kg) and high energy density (943 Wh/kg).

Three-Dimensional Rebar Graphene

Free-standing robust three-dimensional (3D) rebar graphene foams (GFs) were developed by a powder metallurgy template method with multiwalled carbon nanotubes (MWCNTs) as a reinforcing bar, sintered Ni skeletons as a template and catalyst, and sucrose as a solid carbon source. As a reinforcement and bridge between different graphene sheets and carbon shells, MWCNTs improved the thermostability, storage modulus (290.1 kPa) and conductivity (21.82 S cm-1) of 3D GF resulting in a high porosity and structurally stable 3D rebar GF. The 3D rebar GF can support >3150× the foams weight with no irreversible height change, and shows only a ∼25% irreversible height change after loading >8500× the foams weight. The 3D rebar GF also shows stable performance as a highly porous electrode in lithium ion capacitors (LICs) with an energy density of 32 Wh kg-1. After 500 cycles of testing at a high current density of 6.50 mA cm-2, the LIC shows 78% energy density retention. These properties indicate promising applications with 3D rebar GFs in devices requiring stable mechanical and electrochemical properties.

Passive Anti-Icing and Active Deicing Films

Anti-icing and deicing are the two major pathways for suppressing adhesion of ice on surfaces, yet materials with dual capabilities are rare. In this work, we have designed a perfluorododecylated graphene nanoribbon (FDO-GNR) film that takes advantage of both the low polarizability of perfluorinated carbons and the intrinsic conductive nature of graphene nanoribbons. The FDO-GNR films are superhydrophobic with a sheet resistance below 8 kΩ·sq(-1) and then exhibit an anti-icing property that prevents freezing of incoming ice-cold water down to -14 °C. After that point, voltage can be applied to the films to resistively heat and deice the surface. Further a lubricating liquid can be employed to create a slippery surface to improve the films deicing performance. The FDO-GNR films can be easily switched between the superhydrophobic anti-icing mode and the slippery deicing mode by applying the lubricant. A spray-coating method makes it suitable for large-scale applications. The anti-icing and deicing properties render the FDO-GNR films with promise for use in extreme environments.

Laminated Object Manufacturing of 3D‐Printed Laser‐Induced Graphene Foams

Laser-induced graphene (LIG), a graphene structure synthesized by a one-step process through laser treatment of commercial polyimide (PI) film in an ambient atmosphere, has been shown to be a versatile material in applications ranging from energy storage to water treatment. However, the process as developed produces only a 2D product on the PI substrate. Here, a 3D LIG foam printing process is developed on the basis of laminated object manufacturing, a widely used additive-manufacturing technique. A subtractive laser-milling process to yield further refinements to the 3D structures is also developed and shown here. By combining both techniques, various 3D graphene objects are printed. The LIG foams show good electrical conductivity and mechanical strength, as well as viability in various energy storage and flexible electronic sensor applications.

Tip-Sonicated Red Phosphorus-Graphene Nanoribbon Composite for Full Lithium-Ion Batteries

Red phosphorus (RP) is considered a promising anode material for lithium-ion batteries (LIBs) due to its high energy density and low cost. Although RP is electrically insulating, researchers have reduced its particle size and added conductive fillers to improve the electrochemical activity of RP. Here, we report a method for making <1 μm sized RP under ambient conditions by using tip sonication. A specific surfactant solution was used to stabilize the dispersion of <1 μm sized RP. Graphene nanoribbons (GNRs) were added to improve the conductivity. The RP-GNR composite achieved nearly maximum capacity at 0.1C and showed a capacity retention of 96% after 216 cycles at 0.4 C in the half-cell. When combined with a LiCoO2 cathode, the full cell delivered a total capacity of 86 mAh/g after 200 cycles at 0.4C. This study has demonstrated the fabrication of high-performance LIBs using RP in a safe, convenient, and cost-effective manner, and the method might be extended for the preparation of other battery or catalyst materials that are difficult to acquire through bottom-up or top-down approaches.