RESUMEN
Na3 V2 (PO4 )2 O2 F (NVPOF) is widely accepted as advanced cathode material for sodium-ion batteries with high application prospects ascribing to its considerable specific capacity and high working voltage. However, challenges in the full realization of its theoretical potential lie in the novel structural design to accelerate its Na+ diffusivity. Herein, considering the important role of polyanion groups in constituting Na+ diffusion tunnels, boron (B) is doped at the P-site to obtain Na3 V2 (P2- x Bx O8 )O2 F (NVP2- x Bx OF). As evidenced by density functional theory modeling, B-doping induces a dramatic decrease in the bandgap. Delocalization of electrons on the O anions in BO4 tetrahedra is observed in NVP2- x Bx OF, which dramatically lowers the electrostatic resistance experienced by Na+ . As a result, the Na+ diffusivity in the NVP2- x Bx OF cathode has accelerated up to 11 times higher, which secures a high rate property (67.2 mAh g-1 at 60 C) and long cycle stability (95.9% capacity retention at 108.6 mAh g-1 at 10 C after 1000 cycles). The assembled NVP1.90 B0.10 OF//Se-C full cell demonstrates exceptional power/energy density (213.3 W kg-1 @ 426.4 Wh kg-1 and 17970 W kg-1 @ 119.8 Wh kg-1 ) and outstanding capability to withstand long cycles (90.1% capacity retention after 1000 cycles at 105.3 mAh g-1 at 10 C).
RESUMEN
Lithium-sulfur (Li-S) batteries have hitherto attracted dramatic research interests as an optional high-energy output candidate to replace the traditional lithium-ion batteries on account of its high energy density and low cost. Nonetheless, their kinetics arrearage and detrimental "shuttling effect" caused by the migration of soluble lithium polysulfide (LiPS) intermediates severely limit its practical application. Here, by a nonthermal route sulfur is in-situ imprisoned into Co/N-codoped hollow carbon sphere (NC-Co) to construct an integrated S/C-Co-N hollow cathode (S@NC-Co) and directly applied in Li-S batteries, which effectively avoids complex template removal and sulfur infiltration process. The hollow NC-Co sphere not only restricts polysulfides migration via physical confinement but also enhances polysulfides conversion through redox-active electro-catalysis. Moreover, the hollow structure has large cavity offering sufficient space to accommodate volume expansion and excellent conductivity promising efficient electron/charge transfer. As a result, the batteries assembled by the S@NC-Co cathode achieve low polarization and high-rate capability (551 mAh g-1 at 4C). Remarkably, the batteries also present an outstanding long-term durability over 800 cycles at 1C, in which the capacity attenuation is merely 0.06 % per cycle. This work demonstrates a novel strategy in designing hierarchical structures or nanoreactors for electrochemical reactions and energy storage systems.
RESUMEN
Stabilizing Na+ accessibility at high voltage and accelerating Na+ diffusivity are pressing issues to further enhance the energy density of the Na3V2(PO4)3 (NVP) cathode for sodium-ion batteries (SIBs). Herein, by taking a V/Cr solid-solution MXene as a precursor, a facile in-situ reactive transformation strategy to embed Cr-substituted NVP (NVCP) nanocrystals in a dual-carbon network is proposed. Particularly, the substituted Cr atom triggers the accessibility of additional Na+ in NVCP, which is demonstrated by an additional reversible redox plateau at 4.0 V even under extreme conditions. More importantly, the Cr atom alters the Na+ ordering at the Na2 sites with an additional intermediate phase formation during charging/discharging, thus reducing the energy barriers for Na+ migration. As a result, Na+ diffusivity in NVCP accelerates to 2-3 orders of magnitude higher than that of NVP. Eventually, the NVCP cathode exhibits extraordinarily high-rate capability (78 mA g-1 at 200 C and 68975 W kg-1), outstanding cycle stability (over 1500 cycles at 10 C), excellent low-temperature property, and full cell performance.
RESUMEN
Owing to the large surface area and adjustable surface properties, the two-dimensional (2D) MXenes have revealed the great potential in constructing hybrid materials and for Na-ion storage (SIS). In particular, the facilitated Na-ion adsorption, intercalation, and migration on MXenes can be achieved by surface modification. Herein, a new surface modification strategy on MXenes, namely, the reactive surface modification (RSM), is focused and illustrated, while the recent advances in the research of SIS performance based on MXenes and their derivatives obtained from the RSM process are briefly summarized as well. In the second section, the intrinsic surface chemistries of MXenes and their surface-related physicochemical properties are first summarized. Meanwhile, the close relationship between the surface characters and the Na-ion adsorption, intercalation, and migration on MXenes is emphasized. Following the SIS properties of MXenes, the surface-induced SIS property variations, and the SIS performance of RSM MXene-based hybrids are discussed progressively. Finally, the existing challenges and prospects on the RSM MXene-based hybrids for SIS are proposed.