Defect Engineering of Chalcogen-Tailored Oxygen Electrocatalysts for Rechargeable Quasi-Solid-State Zinc-Air Batteries.

A critical bottleneck limiting the performance of rechargeable zinc-air batteries lies in the inefficient bifunctional electrocatalysts for the oxygen reduction and evolution reactions at the air electrodes. Hybridizing transition-metal oxides with functional graphene materials has shown great advantages due to their catalytic synergism. However, both the mediocre catalytic activity of metal oxides and the restricted 2D mass/charge transfer of graphene render these hybrid catalysts inefficient. Here, an effective strategy combining anion substitution, defect engineering, and the dopant effect to address the above two critical issues is shown. This strategy is demonstrated on a hybrid catalyst consisting of sulfur-deficient cobalt oxysulfide single crystals and nitrogen-doped graphene nanomeshes (CoO0.87 S0.13 /GN). The defect chemistries of both oxygen-vacancy-rich, nonstoichiometric cobalt oxysulfides and edge-nitrogen-rich graphene nanomeshes lead to a remarkable improvement in electrocatalytic performance, where CoO0.87 S0.13 /GN exhibits strongly comparable catalytic activity to and much better stability than the best-known benchmark noble-metal catalysts. In application to quasi-solid-state zinc-air batteries, CoO0.87 S0.13 /GN as a freestanding catalyst assembly benefits from both structural integrity and enhanced charge transfer to achieve efficient and very stable cycling operation over 300 cycles with a low discharge-charge voltage gap of 0.77 V at 20 mA cm-2 under ambient conditions.

Hot-Chemistry Structural Phase Transformation in Single-Crystal Chalcogenides for Long-Life Lithium Ion Batteries.

Tuned chalcogenide single crystals rooted in sulfur-doped graphene were prepared by high-temperature solution chemistry. We present a facile route to synthesize a rod-on-sheet-like nanohybrid as an active anode material and demonstrate its superior performance in lithium ion batteries (LIBs). This nanohybrid contains a nanoassembly of one-dimensional (1D) single-crystalline, orthorhombic SnS onto two-dimensional (2D) sulfur-doped graphene. The 1D nanoscaled SnS with the rodlike single-crystalline structure possesses improved transport properties compared to its 2D hexagonal platelike SnS2. Furthermore, we blend this hybrid chalcogenide with biodegradable polymer composite using water as a solvent. Upon drying, the electrodes were subjected to heating in vacuum at 150 °C to induce polymer condensation via formation of carboxylate groups to produce a mechanically robust anode. The LIB using the as-developed anode material can deliver a high volumetric capacity of ∼2350 mA h cm-3 and exhibit superior cycle stability over 1500 cycles as well as a high capacity retention of 85% at a 1 C rate. The excellent battery performance combined with the simplistic, scalable, and green chemistry approach renders this anode material as a very promising candidate for LIB applications.

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 electrode's 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.

In Situ Polymer Graphenization Ingrained with Nanoporosity in a Nitrogenous Electrocatalyst Boosting the Performance of Polymer-Electrolyte-Membrane Fuel Cells.

Rich, porous graphene frameworks decorated with uniformly dispersed active sites are prepared by using polyaniline as a graphene precursor and introducing phenanthroline as a pore-forming agent. The unprecedented fuel-cell performance of this electrocatalyst is linked to the graphene frameworks with vast distribution of pore sizes, which maximizes the active-sites accessibility, facilitates mass-transport properties, and improves the carbon corrosion resistance.

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.

Evidence of covalent synergy in silicon-sulfur-graphene yielding highly efficient and long-life lithium-ion batteries.

Silicon has the potential to revolutionize the energy storage capacities of lithium-ion batteries to meet the ever increasing power demands of next generation technologies. To avoid the operational stability problems of silicon-based anodes, we propose synergistic physicochemical alteration of electrode structures during their design. This capitalizes on covalent interaction of Si nanoparticles with sulfur-doped graphene and with cyclized polyacrylonitrile to provide a robust nanoarchitecture. This hierarchical structure stabilized the solid electrolyte interphase leading to superior reversible capacity of over 1,000 mAh g(-1) for 2,275 cycles at 2 A g(-1). Furthermore, the nanoarchitectured design lowered the contact of the electrolyte to the electrode leading to not only high coulombic efficiency of 99.9% but also maintaining high stability even with high electrode loading associated with 3.4 mAh cm(-2). The excellent performance combined with the simplistic, scalable and non-hazardous approach render the process as a very promising candidate for Li-ion battery technology.

Multigrain platinum nanowires consisting of oriented nanoparticles anchored on sulfur-doped graphene as a highly active and durable oxygen reduction electrocatalyst.

Direct growth of multigrain platinum nanowires on sulfur-doped graphene (PtNW/SG) is reported. The growth mechanism, including Pt nanoparticle nucleation on SG, followed by nanoparticle attachment with orientation along the <111> direction is highlighted. PtNW/SG demonstrates improved Pt mass and specific activity compared with commercial catalysts toward oxygen reduction, in addition to dramatically improved stability through accelerated durability testing.

Subeutectic growth of single-crystal silicon nanowires grown on and wrapped with graphene nanosheets: high-performance anode material for lithium-ion battery.

A novel one-pot synthesis for the subeutectic growth of (111) oriented Si nanowires on an in situ formed nickel nanoparticle catalyst prepared from an inexpensive nickel nitrate precursor is developed. Additionally, anchoring the nickel nanoparticles to a simultaneously reduced graphene oxide support created synergy between the individual components of the c-SiNW-G composite, which greatly improved the reversible charge capacity and it is retention at high current density when applied as an anode for a Li-ion battery. The c-SiNW-G electrodes for Li-ion battery achieved excellent high-rate performance, producing a stable reversible capacity of 550 mAh g(-1) after 100 cycles at 6.8 A g(-1) (78% of that at 0.1 A g(-1)). Thus, with further development this process creates an important building block for a new wave of low-cost silicon nanowire materials and a promising avenue for high rate Li-ion batteries.

Engineered Si electrode nanoarchitecture: a scalable postfabrication treatment for the production of next-generation Li-ion batteries.

A novel, economical flash heat treatment of the fabricated silicon based electrodes is introduced to boost the performance and cycle capability of Li-ion batteries. The treatment reveals a high mass fraction of Si, improved interfacial contact, synergistic SiO2/C coating, and a conductive cellular network for improved conductivity, as well as flexibility for stress compensation. The enhanced electrodes achieve a first cycle efficiency of ∼84% and a maximum charge capacity of 3525 mA h g(-1), almost 84% of silicon's theoretical maximum. Further, a stable reversible charge capacity of 1150 mA h g(-1) at 1.2 A g(-1) can be achieved over 500 cycles. Thus, the flash heat treatment method introduces a promising avenue for the production of industrially viable, next-generation Li-ion batteries.