Hollow porous carbon nanospheres containing polar cobalt sulfide (Co9S8) nanocrystals as electrocatalytic interlayers for the reutilization of polysulfide in lithium-sulfur batteries.

HYPOTHESIS: The introduction of functional interlayers for efficient anchoring of lithium polysulfides has received significant attention worldwide. EXPERIMENTS: A facile wet-chemical method was adopted to obtain hollow porous carbon nanospheres (HPCNSs) impregnated with metallic and polar cobalt sulfide (Co9S8) nanocrystals (abbreviated as "Co9S8@HPCNS"). The prepared nanocrystals were employed as electrocatalytic interlayers via separator coating for the efficient capture and reutilization of polysulfide species in Li-S batteries. The HPCNSs were synthesized via the polymerization method followed by carbonization and template removal. The Co9S8 nanocrystals were impregnated inside the HPCNSs, followed by heat treatment in a reducing atmosphere. FINDINGS: The porous structure of the CNS enables the efficient percolation of the electrolyte, in addition to accommodating unwanted volume fluctuations during redox processes. Furthermore, the metallic Co9S8 nanocrystals improve the electronic conductivity and enhance the polarity of the CNS towards the polysulfide. Correspondingly, the Li-S cells featuring Co9S8@HPCNS as electrocatalytic interlayers and regular sulfur (S) electrodes display improved electrochemical performance such as reasonable rate performance and prolonged cycling stability at different current rates (0.1, 0.5, and 1.0 C). Therefore, we anticipate that the rational design strategy proposed herein will provide significant insights into the synthesis of advanced materials for various energy storage applications.

Porous Microspheres Comprising CoSe2 Nanorods Coated with N-Doped Graphitic C and Polydopamine-Derived C as Anodes for Long-Lived Na-Ion Batteries.

Metal-organic framework-templated nitrogen-doped graphitic carbon (NGC) and polydopamine-derived carbon (PDA-derived C)-double coated one-dimensional CoSe2 nanorods supported highly porous three-dimensional microspheres are introduced as anodes for excellent Na-ion batteries, particularly with long-lived cycle under carbonate-based electrolyte system. The microspheres uniformly composed of ZIF-67 polyhedrons and polystyrene nanobeads (ϕ = 40 nm) are synthesized using the facile spray pyrolysis technique, followed by the selenization process (P-CoSe2@NGC NR). Further, the PDA-derived C-coated microspheres are obtained using a solution-based coating approach and the subsequent carbonization process (P-CoSe2@PDA-C NR). The rational synthesis approach benefited from the synergistic effects of dual carbon coating, resulting in a highly conductive and porous nanostructure that could facilitate rapid diffusion of charge species along with efficient electrolyte infiltration and effectively channelize the volume stress. Consequently, the prepared nanostructure exhibits extraordinary electrochemical performance, particularly the ultra-long cycle life stability. For instance, the advanced anode has a discharge capacity of 291 (1000th cycle, average capacity decay of 0.017%) and 142 mAh g-1 (5000th cycle, average capacity decay of 0.011%) at a current density of 0.5 and 2.0 A g-1, respectively.

Nanofibers Comprising Interconnected Chain-Like Hollow N-Doped C Nanocages as 3D Free-Standing Cathodes for Li-S Batteries with Super-High Sulfur Content and Lean Electrolyte/Sulfur Ratio.

The development of a suitable cathode host that withstands high sulfur content/loading and low electrolyte/sulfur (E/S) ratio is particularly important for practically sustainable Li-S batteries. Herein, a facile approach is utilized to prepare free-standing 3D cathode substrates comprising nitrogen-doped carbon (N-C) scaffold and metal-organic framework derived interconnected chain-like hollow N-C nanocages, forming a highly porous N-C nanofiber (HP-N-CNF) framework. The N-C skeleton provides highly conductive pathways for fast lithium ion/electron diffusion. The hollow interconnected N-C nanocages not only offer enough space to absorb a high volume of active material but also effectively channelize severe volume stress during the electrochemical performance. The Li-S cell utilizing HP-N-CNF as cathode host displays exceptional battery parameters with high effective sulfur content (83.2 wt%), ultrahigh sulfur loading (14.3 mg cm-2 ), and low E/S ratio (6.8 µL mg-1 ). The Li-S cell exhibits a maximum areal capacity of 12.2 mAh cm-2 which stabilizes at ≈5.5 mAh cm-2 after the 130th cycle at 0.05 C-rate and is well above the theoretical threshold. Therefore, the proposed unique nanostructure synthesis approach would open new frontiers for developing more realistic and sustainable host materials with feasible battery parameters for various energy storage applications.

Rational Design of Perforated Bimetallic (Ni, Mo) Sulfides/N-doped Graphitic Carbon Composite Microspheres as Anode Materials for Superior Na-Ion Batteries.

Highly conductive 3D ordered mesoporous Ni7 S6 -MoS2 /N-doped graphitic carbon (NGC) composite (P-NiMoS/C) microspheres are prepared as anode materials for Na-ion batteries. The rationally designed nanostructure comprises stable Ni7 S6 - and MoS2 -phases along with the homogeneously distributed ordered mesopores (ϕ = 50 nm) over the external and internal structures generated through thermal decomposition of polystyrene nanobeads (ϕ = 100 nm). Therefore, the P-NiMoS/C microspheres deliver initial discharge capacities of 662, 419, 373, 300, 231, 181, and 146 mA h g-1 at current densities of 0.5, 1, 2, 4, 6, 8, and 10 A g-1 , respectively. Furthermore, P-NiMoS/C exhibits a stable discharge capacity of 444 mA h g-1 at the end of the 150th cycle at a current density of 0.5 A g-1 , indicating higher cycling stability than the filled, that is, non-mesoporous, Ni3 S2 -MoS2 /NGC (F-NiMoS/C) microspheres and filled carbon-free Ni3 S2 -MoS2 (F-NiMoS) microspheres. The superior electrochemical performance of P-NiMoS/C microspheres is attributed to the rapid Na+ ion diffusion, alleviation of severe volume stress during prolonged cycling, and higher electrical conductivity of NGC, which results in fast charge transfer during the redox processes. The results in the present study can provide fundamental knowledge for the development of multicomponent, porous, and highly conductive anodes for various applications.

Controlling the Voltage Window for Improved Cycling Performance of SnO2 as Anode Material for Lithium-Ion Batteries.

Transition metal oxide materials with high theoretical capacities have been studied as substitutes for commercial graphite in lithiumion batteries. Among these, SnO2 is a promising alloying reaction-based anode material. However, the problem of rapid capacity fading in SnO2 due to volume variation during the alloying/dealloying processes must be solved. The lithiation of SnO2 results in the formation of a Li2O matrix. Herein, the volume variation of SnO2 was suppressed by controlling the voltage window to 1 V to prevent the delithiation reaction between Li2O and Sn. Using this strategy the unreacted Li2O matrix was enriched with metallic Sn particles, thereby providing a pathway for lithium ions. The specific capacity decay in the voltage window of 0.05-3 V was 1.8% per cycle. However, the specific capacity decay was improved to 0.04% per cycle after the voltage window was restricted (in the range of 0.05-1 V). This strategy resulted in a specific capacity of 374.7 mAh g-1 at 0.1 C after 40 cycles for the SnO2 anode.

Hierarchically Well-Developed Porous Graphene Nanofibers Comprising N-Doped Graphitic C-Coated Cobalt Oxide Hollow Nanospheres As Anodes for High-Rate Li-Ion Batteries.

Hierarchically well-developed porous graphene nanofibers comprising N-doped graphitic C (NGC)-coated cobalt oxide hollow nanospheres are introduced as anodes for high-rate Li-ion batteries. For this, three strategies, comprising the Kirkendall effect, metal-organic frameworks, and compositing with highly conductive C, are applied to the 1D architecture. In particular, NGC layers are coated on cobalt oxide hollow nanospheres as a primary transport path of electrons followed by graphene-nanonetwork-constituting nanofibers as a continuous and secondary electron transport path. Superior cycling performance is achieved, as the unique nanostructure delivers a discharge capacity of 823 mAh g-1 after 500 cycles at 3.0 A g-1 with a low decay rate of 0.092% per cycle. The rate capability is also noteworthy as the structure exhibits high discharge capacities of 1035, 929, 847, 787, 747, 703, 672, 650, 625, 610, 570, 537, 475, 422, 294, and 222 mAh g-1 at current densities of 0.5, 1.5, 3, 5, 7, 10, 12, 15, 18, 20, 25, 30, 40, 50, 80, and 100 A g-1 , respectively. In view of the highly efficient Li+ ion/electron diffusion and high structural stability, the present nanostructuring strategy has a huge potential in opening new frontiers for high-rate and long-lived stable energy storage systems.

Electrochemical Properties of Na0.66V4O10 Nanostructures as Cathode Material in Rechargeable Batteries for Energy Storage Applications.

We report the electrochemical performance of nanostructures of Na0.66V4O10 as cathode material for rechargeable batteries. The Rietveld refinement of room-temperature X-ray diffraction pattern shows the monoclinic phase with C2/m space group. The cyclic voltammetry curves of prepared half-cells exhibit redox peaks at 3.1 and 2.6 V, which are due to two-phase transition reaction between V5+/4+ and can be assigned to the single-step deintercalation/intercalation of Na ion. We observe a good cycling stability with specific discharge capacity (measured vs Na+/Na) between 80 (±2) and 30 (±2) mAh g-1 at current densities of 3 and 50 mA g-1, respectively. The electrochemical performance of Na0.66V4O10 electrode was also tested with Li anode, which showed higher capacity but decayed faster than Na. Using density functional theory, we calculate the Na vacancy formation energies: 3.37 eV in the bulk of the material and 2.52 eV on the (100) surface, which underlines the importance of nanostructures.