Nonstoichiometric Scandium Oxide Hybridized in N-Doped Porous Graphitic Carbon Promotes the Rate Capability of Lithium-Sulfur Batteries.

Nonstoichiometric compounds are widely used in contemporary energy technologies due to their high surface polarity, tailored electronic structure, high electrical conductivity, and other enhanced properties. However, the preparation of such nonstoichiometric compounds can be complicated and, in some cases, uncontrollable and dangerous. Here, we report a "one-pot" strategy for synthesizing N-doped porous graphitic carbon that is hybridized with nonstoichiometric scandium oxide (denoted as ScO0.95@N-PGC) and show that the composite significantly promotes sulfur cathode kinetics in lithium-sulfur (Li-S) batteries. The synthesis of the ScO0.95@N-PGC composite entails heating a porous dry gel that consists of a C source (glucose), a N source (dicyandiamide), and a Sc source (Sc(NO3)3·H2O). Thermally decomposing the dicyandiamide creates a highly reductive atmosphere that simultaneously affords the hypoxic state of the ScO0.95 and dopes the carbon matrix with nitrogen. Density functional theory reveals the presence of oxygen vacancies that enable the ScO0.95 crystals to function as excellent electrical conductors, exhibit enhanced adsorption toward polysulfides, and accelerate the cathode reactions by lowering the corresponding activation energies. Moreover, Li-S cells prepared from the ScO0.95@N-PGC composite display a high specific capacity (1046 mA h g-1 at 0.5 C), an outstanding cycling stability (641 mA h g-1 after 1000 charge-discharge cycles at 0.5 C, a capacity decay of 0.038% per cycle), and a particularly outstanding rate capability (438 mA h g-1 at 8 C). The methodology described establishes a sustainable approach for synthesizing nonstoichiometric compounds while broadening their potential utility in a broad range of energy technologies.

P-Doping a Porous Carbon Host Promotes the Lithium Storage Performance of Red Phosphorus.

Red phosphorus (RP) is a promising anode material for use in lithium-ion batteries (LIBs) due to its high theoretical specific capacity (2596 mA h g-1). However, the practical use of RP-based anodes has been challenged by the material's low intrinsic electrical conductivity and poor structural stability during lithiation. Here, we describe a phosphorus-doped porous carbon (P-PC) and disclose how the dopant improves the Li storage performance of RP that was incorporated into the P-PC (designated as RP@P-PC). P-doping porous carbon was achieved using an in situ method wherein the heteroatom was added as the porous carbon was being formed. The phosphorus dopant effectively improves the interfacial properties of the carbon matrix as subsequent RP infusion results in high loadings, small particle sizes, and uniform distribution. In half-cells, an RP@P-PC composite was found to exhibit outstanding performance in terms of the ability to store and utilize Li. The device delivered a high specific capacitance and rate capability (1848 and 1111 mA h g-1 at 0.1 and 10.0 A g-1, respectively) as well as excellent cycling stability (1022 mA h g-1 after 800 cycles at 2.0 A g-1). Exceptional performance metrics were also measured when the RP@P-PC was used as an anode material in full cells that contained lithium iron phosphate as the cathode material. The methodology described can be extended to the preparation of other P-doped carbon materials that are employed in contemporary energy storage applications.

Single-Atom Catalyst Aggregates: Size-Matching is Critical to Electrocatalytic Performance in Sulfur Cathodes.

Electrocatalysis is critical to the performance displayed by sulfur cathodes. However, the constituent electrocatalysts and the sulfur reactants have vastly different molecular sizes, which ultimately restrict electrocatalysis efficiency and hamper device performance. Herein, the authors report that aggregates of cobalt single-atom catalysts (SACs) attached to graphene via porphyrins can overcome the challenges associated with the catalyst/reactant size mismatch. Atomic-resolution transmission electron microscopy and X-ray absorption spectroscopy measurements show that the Co atoms present in the SAC aggregates exist as single atoms with spatially resolved dimensions that are commensurate the sulfur species found in sulfur cathodes and thus fully accessible to enable 100% atomic utilization efficiency in electrocatalysis. Density functional theory calculations demonstrate that the Co SAC aggregates can interact with the sulfur species in a synergistic manner that enhances the electrocatalytic effect and promote the performance of sulfur cathodes. For example, Li-S cells prepared from the Co SAC aggregates exhibit outstanding capacity retention (i.e., 505 mA h g-1 at 0.5 C after 600 cycles) and excellent rate capability (i.e., 648 mA h g-1 at 6 C). An ultrahigh area specific capacity of 12.52 mA h cm-2 is achieved at a high sulfur loading of 11.8 mg cm-2 .

Regulating Lithium Plating and Stripping by Using Vertically Aligned Graphene/CNT Channels Decorated with ZnO Particles.

Lithium (Li) metal is regarded as the ultimate anode material for use in Li batteries due to its high theoretical capacity (3860 mA h g-1 ). However, the Li dendrites that are generated during iterative Li plating/stripping cycles cause poor cycling stability and even present safety risks, and thus severely handicap the commercial utility of Li metal anodes. Herein, we describe a graphene and carbon nanotube (CNT)-based Li host material that features vertically aligned channels with attached ZnO particles (designated ZnO@G-CNT-C) and show that the material effectively regulates Li plating and stripping. ZnO@G-CNT-C is prepared from an aqueous suspension of Zn(OAc)2 , CNTs, and graphene oxide by using ice to template channel growth. ZnO@G-CNT-C was found to be mechanically robust and capable of guiding Li deposition on the inner walls of the channels without the formation of Li dendrites. When used as an electrode, the material exhibits relatively low polarization for Li plating, fast Li-ion diffusion, and high Coulombic efficiency, even over hundreds of Li plating/stripping cycles. Moreover, full cells prepared with ZnO@G-CNT-C as Li host and LiFePO4 as cathode exhibit outstanding performance in terms of specific capacity (155.9 mA h g-1 at 0.5 C), rate performance (91.8 mA h g-1 at 4 C), cycling stability (109.4 mA h g-1 at 0.5 C after 800 cycles). The methodology described can be readily adapted to enable the use of carbon-based electrodes with well-defined channels in a wide range of contemporary applications that pertain to energy storage and delivery.

Ice-Templated Large-Scale Preparation of Two-Dimensional Sheets of Conjugated Polymers: Thickness-Independent Flexible Supercapacitance.

Two-dimensional (2D) organic materials hold great promise for use in a multitude of contemporary applications due to their outstanding chemical and physical properties. Herein, 2D sheets of poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) are prepared from a commercially available PEDOT:PSS suspension using ice as a template. The 2D PEDOT:PSS sheets grow in the boundaries of ice crystals as the polymers are "squeezed" out of the suspension when the water solidifies. The mechanical robustness of the sheets can be enhanced by incorporating WO3 nanowires, and the PSS component can be conveniently removed with a concentrated solution of H2SO4 to afford stable suspensions of PEDOT or WO3@PEDOT sheets, either of which can be converted into flexible films with tunable thicknesses via filtration. Swagelok- or pouch-type supercapacitor devices prepared from the WO3@PEDOT films exhibit outstanding energy-storage characteristics, including high rate capability, thickness-independent energy storage (e.g., 701 mF cm-2 is achieved with a 1-mm-thick film), high resistance toward mechanical deformation, and good cycling stability. Additionally, a high energy density of 0.083 mWh cm-2 is measured for a device prepared using a 1-mm-thick film at a high power density of 10 mW cm-2. The methodology described establishes an efficient and readily scalable approach for accessing 2D organic sheets.