Min Ho Seo

Shape-controlled octahedral cobalt disulfide nanoparticles supported on nitrogen and sulfur-doped graphene/carbon nanotube composites for oxygen reduction in acidic electrolyte

Replacement of expensive platinum-based catalysts at the cathode of fuel cells by low-cost alternatives represents an important milestone to achieve significant system cost reductions. In this work, single crystal cobalt disulfide (CoS2) octahedral nanoparticles supported on graphene/carbon nanotube composites were prepared as oxygen reduction reaction (ORR) catalysts in acidic electrolyte. During the simplistic, one-pot solvothermal synthesis, the nanostructured carbon supports were also simultaneously doped with nitrogen and sulfur. Time dependent studies elucidated the growth process of the {111} facet encased octahedra that could only be prepared when carbon support materials were incorporated into the reaction mixture. Through computational simulations, the shape directed growth process was found to be driven thermodynamically towards surface energy minimization. Control experiments and spectroscopy characterization were also used to investigate the occurrence and nature of nitrogen and sulfur doping into the graphitic structure of the graphene/carbon nanotube composite support. The impact of carbon support on ORR activity was clear, with the graphene/carbon nanotube composite supported CoS2 octahedra (CoS2-CG) outperforming CoS2 supported on just graphene or carbon nanotubes. Additionally, CoS2-CG provided an on-set potential (0.78 V vs. RHE) and half-wave potential (0.66 V vs. RHE) that was 60 mV and 150 mV higher than the CoS2 particle agglomerates formed when no carbon support was included during catalyst preparation. This improved activity can be attributed to the beneficial properties of the nitrogen and sulfur doped graphene/carbon nanotube composite support, and also may arise due to the more favourable oxygen adsorption on the (111) surface of the octahedral particles predicted by theoretical calculations. By combining the synergistic properties of the graphene/carbon nanotube composite and unique shape controlled single crystal CoS2 nanoparticles, CoS2-CG is presented as an emerging catalyst for the ORR in fuel cells.

Perovskite–Nitrogen-Doped Carbon Nanotube Composite as Bifunctional Catalysts for Rechargeable Lithium–Air Batteries

Developing an effective bifunctional catalyst is a significant issue, as rechargeable metal-air batteries are very attractive for future energy systems. In this study, a facile one-pot process is introduced to prepare an advanced bifunctional catalyst (op-LN) incorporating nitrogen-doped carbon nanotubes (NCNTs) into perovskite La0.5 Sr0.5 Co0.8 Fe0.2 O3 nanoparticles (LSCF-NPs). Confirmed by half-cell testing, op-LN exhibits synergistic effects of LSCF-NP and NCNT with excellent bifunctionality for both the oxygen reduction reaction and the oxygen evolution reaction. Furthermore, op-LN exhibits comparable performances in these reactions to Pt/C and Ir/C, respectively, which highlights its potential for use as a commercially viable bifunctional catalyst. Moreover, the results obtained by testing op-LN in a practical Li-air battery demonstrate improved and complementary charge/discharge performance compared to those of LSCF-NP and NCNT, and this confirms that simply prepared op-LN is a promising candidate as a highly effective bifunctional catalyst for rechargeable metal-air batteries.

3D Ordered Mesoporous Bifunctional Oxygen Catalyst for Electrically Rechargeable Zinc-Air Batteries.

To enhance energy efficiency and durability, a highly active and durable 3D ordered mesoporous cobalt oxide framework has been developed for rechargeable zinc-air batteries. The bifunctional air electrode consisting of 3DOM Co3 O4 having high active surface area and robust structure, results in superior charge and discharge battery voltages, and durable performance for electrically rechargeable zinc-air batteries.

First principles computational study on the electrochemical stability of Pt-Co nanocatalysts.

Using density functional theory (DFT) calculations, we identify the thermodynamically stable configurations of Pt-Co alloy nanoparticles of varying Co compositions and particle sizes. Our results indicate that the most thermodynamically stable structure is a shell-by-shell configuration where the Pt atom only shell and the Co only shell alternately stack and the outermost shell consists of a Pt skin layer. DFT calculations show that the structure has substantially higher dissolution potential of the outermost Pt shell compared with pure Pt nanoparticles of approximately the same size. Furthermore, our DFT calculations also propose that the shell-by-shell structure shows much better oxygen reduction reaction (ORR) activity than conventional bulk or nanoparticles of pure Pt. These novel catalyst properties can be changed when the surfaces are adsorbed with oxygen atoms via selective segregation followed by the electrochemical dissolution of the alloyed Co atoms. However, these phenomena are thermodynamically not plausible if the chemical potentials of oxygen are controlled below a certain level. Therefore, we propose that the shell-by-shell structures are promising candidates for highly functional catalysts in fuel cell applications.

Sulfur Nanogranular Film-Coated Three-Dimensional Graphene Sponge-Based High Power Lithium Sulfur Battery

To meet the requirements of both high energy and power density with cycle durability of modern EVs, we prepared a novel nanosulfur granular assembled film coated on the three-dimensional graphene sponge (3D-GS) composite as a high-performance active material for rechargeable lithium sulfur batteries. Instead of conventional graphene powder, three-dimensional rGO sponge (3D-rGO) is employed for the composite synthesis, resulting in a sulfur film directly in contact with the underlying graphene layer. This significantly improves the overall electrical conductivity, strategically addressing challenges of conventional composites of low sulfur utilization and dissolution of polysulfides. Additionally, the synthesis mechanism of 3D-GS is elucidated by XPS and DFT analyses, where replacement of hydroxyl group of 3D-rGO sponge by sulfur (S8) is found to be thermodynamically favorable. As expected, 3D-GS demonstrates outstanding discharge capacity of 1080 mAh g(-1) at a 0.1C rate, and 86.2% capacity retention even after 500 cycles at a 1.0C rate.

Highly Active and Durable Nanocrystal-Decorated Bifunctional Electrocatalyst for Rechargeable Zinc-Air Batteries.

A highly active and durable bifunctional electrocatalyst that consists of cobalt oxide nanocrystals (Co3 O4 NC) decorated on the surface of N-doped carbon nanotubes (N-CNT) is introduced as effective electrode material for electrically rechargeable zinc-air batteries. This active hybrid catalyst is synthesized by a facile surfactant-assisted method to produce Co3 O4 NC that are then decorated on the surface of N-CNT through hydrophobic attraction. Confirmed by half-cell testing, Co3 O4 NC/N-CNT demonstrates superior oxygen reduction and oxygen evolution catalytic activities and has a superior electrochemical stability compared to Pt/C and Ir/C. Furthermore, rechargeable zinc-air battery testing of Co3 O4 NC/N-CNT reveals superior galvanodynamic charge and discharge voltages with a significantly extended cycle life of over 100 h, which suggests its potential as a replacement for precious-metal-based catalysts for electric vehicles and grid energy storage applications.

Toward new fuel cell support materials: a theoretical and experimental study of nitrogen-doped graphene.

Nano-scale Pt particles are often reported to be more electrochemically active and stable in a fuel cell if properly displaced on support materials; however, the factors that affect their activity and stability are not well understood. We applied first-principles calculations and experimental measurements to well-defined model systems of N-doped graphene supports (N-GNS) to reveal the fundamental mechanisms that control the catalytic properties and structural integrity of nano-scale Pt particles. DFT calculations predict thermodynamic and electrochemical interactions between N-GNS and Pt nanoparticles in the methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR). Moreover, the dissolution potentials of the Pt nanoparticles supported on GNS and N-GNS catalysts are calculated under acidic conditions. Our results provide insight into the design of new support materials for enhanced catalytic efficiency and long-term stability.

Design of an active and durable catalyst for oxygen reduction reactions using encapsulated Cu with N-doped carbon shells (Cu@N-C) activated by CO2 treatment

Cu@N-C with the Cu particles encapsulated in N-doped carbon shells, which was activated by CO2 treatment, is an excellent electrocatalyst for the oxygen reduction reaction (ORR) with a high activity and durability.

Carbon-Coated Silicon Nanowires on Carbon Fabric as Self-Supported Electrodes for Flexible Lithium-Ion Batteries

A novel self-supported electrode with long cycling life and high mass loading was developed based on carbon-coated Si nanowires grown in situ on highly conductive and flexible carbon fabric substrates through a nickel-catalyzed one-pot atmospheric pressure chemical vapor deposition. The high-quality carbon coated Si nanowires resulted in high reversible specific capacity (∼3500 mA h g-1 at 100 mA g-1), while the three-dimensional electrodes unique architecture leads to a significantly improved robustness and a high degree of electrode stability. An exceptionally long cyclability with a capacity retention of ∼66% over 500 cycles at 1.0 A g-1 was achieved. The controllable high mass loading enables an electrode with extremely high areal capacity of ∼5.0 mA h cm-2. Such a scalable electrode fabrication technology and the high-performance electrodes hold great promise in future practical applications in high energy density lithium-ion batteries.

Chemisorption of polysulfides through redox reactions with organic molecules for lithium–sulfur batteries

Lithium–sulfur battery possesses high energy density but suffers from severe capacity fading due to the dissolution of lithium polysulfides. Novel design and mechanisms to encapsulate lithium polysulfides are greatly desired by high-performance lithium–sulfur batteries towards practical applications. Herein, we report a strategy of utilizing anthraquinone, a natural abundant organic molecule, to suppress dissolution and diffusion of polysulfides species through redox reactions during cycling. The keto groups of anthraquinone play a critical role in forming strong Lewis acid-based chemical bonding. This mechanism leads to a long cycling stability of sulfur-based electrodes. With a high sulfur content of ~73%, a low capacity decay of 0.019% per cycle for 300 cycles and retention of 81.7% over 500 cycles at 0.5 C rate can be achieved. This finding and understanding paves an alternative avenue for the future design of sulfur–based cathodes toward the practical application of lithium–sulfur batteries.Novel cathode design holds the key to enabling high performance lithium-sulfur batteries. Here the authors utilize anthraquinone to chemically stabilize polysulfides, revealing that the keto groups of anthraquinone play a critical role in forming strong Lewis acid-based chemical bonding.