Jibo Zhang

High-Performance Pseudocapacitive Microsupercapacitors from Laser-Induced Graphene.

All-solid-state, flexible, symmetric, and asymmetric microsupercapacitors are fabricated by a simple method in a scalable fashion from laser-induced graphene on commercial polyimide films, followed by electrodeposition of pseudocapacitive materials on the interdigitated in-plane architectures. These microsupercapacitors demonstrate comparable energy density to commercial lithium thin-film batteries, yet exhibit more than two orders of magnitude higher power density with good mechanical flexibility.

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.

Single-Atomic Ruthenium Catalytic Sites on Nitrogen-Doped Graphene for Oxygen Reduction Reaction in Acidic Medium

The cathodic oxygen reduction reaction (ORR) is essential in the electrochemical energy conversion of fuel cells. Here, through the NH3 atmosphere annealing of a graphene oxide (GO) precursor containing trace amounts of Ru, we have synthesized atomically dispersed Ru on nitrogen-doped graphene that performs as an electrocatalyst for the ORR in acidic medium. The Ru/nitrogen-doped GO catalyst exhibits excellent four-electron ORR activity, offering onset and half-wave potentials of 0.89 and 0.75 V, respectively, vs a reversible hydrogen electrode (RHE) in 0.1 M HClO4, together with better durability and tolerance toward methanol and carbon monoxide poisoning than seen in commercial Pt/C catalysts. X-ray adsorption fine structure analysis and aberration-corrected high-angle annular dark-field scanning transmission electron microscopy are performed and indicate that the chemical structure of Ru is predominantly composed of isolated Ru atoms coordinated with nitrogen atoms on the graphene substrate. Furthermore, a density function theory study of the ORR mechanism suggests that a Ru-oxo-N4 structure appears to be responsible for the ORR catalytic activity in the acidic medium. These findings provide a route for the design of efficient ORR single-atom catalysts.

Laser‐Induced Graphene in Controlled Atmospheres: From Superhydrophilic to Superhydrophobic Surfaces

The modification of graphene-based materials is an important topic in the field of materials research. This study aims to expand the range of properties for laser-induced graphene (LIG), specifically to tune the hydrophobicity and hydrophilicity of the LIG surfaces. While LIG is normally prepared in the air, here, using selected gas atmospheres, a large change in the water contact angle on the as-prepared LIG surfaces has been observed, from 0° (superhydrophilic) when using O2 or air, to >150° (superhydrophobic) when using Ar or H2 . Characterization of the newly derived surfaces shows that the different wetting properties are due to the surface morphology and chemical composition of the LIG. Applications of the superhydrophobic LIG are shown in oil/water separation as well as anti-icing surfaces, while the versatility of the controlled atmosphere chamber fabrication method is demonstrated through the improved microsupercapacitor performance generated from LIG films prepared in an O2 atmosphere.

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.

Laser-Induced Graphene Formation on Wood

Wood as a renewable naturally occurring resource has been the focus of much research and commercial interests in applications ranging from building construction to chemicals production. Here, a facile approach is reported to transform wood into hierarchical porous graphene using CO2 laser scribing. Studies reveal that the crosslinked lignocellulose structure inherent in wood with higher lignin content is more favorable for the generation of high-quality graphene than wood with lower lignin content. Because of its high electrical conductivity (≈10 Ω per square), graphene patterned on wood surfaces can be readily fabricated into various high-performance devices, such as hydrogen evolution and oxygen evolution electrodes for overall water splitting with high reaction rates at low overpotentials, and supercapacitors for energy storage with high capacitance. The versatility of this technique in formation of multifunctional wood hybrids can inspire both research and industrial interest in the development of wood-derived graphene materials and their nanodevices.

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.

Sulfur-Doped Laser-Induced Porous Graphene Derived from Polysulfone-Class Polymers and Membranes

Graphene based materials have profoundly impacted research in nanotechnology, and this has significantly advanced biomedical, electronics, energy, and environmental applications. Laser-induced graphene (LIG) is made photothermally and has enabled a rapid route for graphene layers on polyimide surfaces. However, polysulfone (PSU), poly(ether sulfone) (PES), and polyphenylsulfone (PPSU) are highly used in numerous applications including medical, energy, and water treatment and they are critical components of polymer membranes. Here we show LIG fabrication on PSU, PES, and PPSU resulting in conformal sulfur-doped porous graphene embedded in polymer dense films or porous substrates using reagent- and solvent-free methods in a single step. We demonstrate the applicability as flexible electrodes with enhanced electrocatalytic hydrogen peroxide generation, as antifouling surfaces and as antimicrobial hybrid membrane-LIG porous filters. The properties and surface morphology of the conductive PSU-, PES-, and PPSU-LIG could be modulated using variable laser duty cycles. The LIG electrodes showed enhanced hydrogen peroxide generation compared to LIG made on polyimide, and showed exceptional biofilm resistance and potent antimicrobial killing effects when treated with Pseudomonas aeruginosa and mixed bacterial culture. The hybrid PES-LIG membrane-electrode ensured complete elimination of bacterial viability in the permeate (6 log reduction), in a flow-through filtration mode at a water flux of ∼500 L m-2 h-1 (2.5 V) and at ∼22 000 L m-2 h-1 (20 V). Due to the widespread use of PSU, PES, and PPSU in modern society, these functional PSU-, PES-, and PPSU-LIG surfaces have great potential to be incorporated into biomedical, electronic, energy and environmental devices and technologies.

Efficient Water-Splitting Electrodes Based on Laser-Induced Graphene

Electrically splitting water to H2 and O2 is a preferred method for energy storage as long as no CO2 is emitted during the supplied electrical input. Here we report a laser-induced graphene (LIG) process to fabricate efficient catalytic electrodes on opposing faces of a plastic sheet, for the generation of both H2 and O2. The high porosity and electrical conductivity of LIG facilitates the efficient contact and charge transfer with the requisite electrolyte. The LIG-based electrodes exhibit high performance for hydrogen evolution reaction and oxygen evolution reaction with excellent long-term stability. The overpotential reaches 100 mA/cm2 for HER, and OER is as low as 214 and 380 mV with relatively low Tafel slopes of 54 and 49 mV/dec, respectively. By serial connecting of the electrodes with a power source in an O-ring setup, H2 and O2 are simultaneously generated on either side of the plastic sheet at a current density of 10 mA/cm2 at 1.66 V and can thereby be selectively captured. The demonstration provides a promising route to simple, efficient, and complete water splitting.

Oxidized Laser‐Induced Graphene for Efficient Oxygen Electrocatalysis

An efficient metal-free catalyst is presented for oxygen evolution and reduction based on oxidized laser-induced graphene (LIG-O). The oxidation of LIG by O2 plasma to form LIG-O boosts its performance in the oxygen evolution reaction (OER), exhibiting a low onset potential of 260 mV with a low Tafel slope of 49 mV dec-1 , as well as an increased activity for the oxygen reduction reaction. Additionally, LIG-O shows unexpectedly high activity in catalyzing Li2 O2 decomposition in Li-O2 batteries. The overpotential upon charging is decreased from 1.01 V in LIG to 0.63 V in LIG-O. The oxygen-containing groups make essential contributions, not only by providing the active sites, but also by facilitating the adsorption of OER intermediates and lowering the activation energy.