Red phosphorus (P) has attracted intense attention as promising anode material for high-energy density sodium-ion batteries (NIBs), owing to its high sodium storage theoretical capacity (2595 mAh g ). Nevertheless, natural insulating property and large volume variation of red P during cycling result in extremely low electrochemical activity, leading to poor electrochemical performance. Herein, the authors demonstrate a rational strategy to improve sodium storage performance of red P by confining nanosized amorphous red P into zeolitic imidazolate framework-8 (ZIF-8) -derived nitrogen-doped microporous carbon matrix (denoted as P@N-MPC). When used as anode for NIBs, the P@N-MPC composite displays a high reversible specific capacity of ≈600 mAh g at 0.15 A g and improved rate capacity (≈450 mAh g at 1 A g after 1000 cycles with an extremely low capacity fading rate of 0.02% per cycle). The superior sodium storage performance of the P@N-MPC is mainly attributed to the novel structure. The N-doped porous carbon with sub-1 nm micropore facilitates the rapid diffusion of organic electrolyte ions and improves the conductivity of the encapsulated red P. Furthermore, the porous carbon matrix can buffer the volume change of red P during repeat sodiation/desodiation process, keeping the structure intact after long cycle life.
Potassium-ion
batteries (KIBs) are a promising alternative to lithium-ion
batteries (LIBs) for large-scale renewable energy storage owning to
the natural abundance and low cost of potassium. However, the biggest
challenge for KIBs application lies in the lack of suitable electrode
materials that can deliver long cycle life and high reversible capacity.
In this work, we realized unprecedented long cycle life with high
reversible capacity (465 mAh g–1 at 2 A g–1 after 800 cycles) as well as outstanding rate capability (342 mAh
g–1 at 5 A g–1) for KIBs by embedding
red P into free-standing nitrogen-doped porous hollow carbon nanofibers
(red P@N-PHCNFs). This design circumvents the problems of pulverization
and aggregation of P particles. The in situ transmission
electron microscopy (TEM) investigation reveals the structural robustness
of the composite fibers during potassiation. The formation of P–C
chemical bonds as well as nitrogen doping in the carbon matrix can
facilitate the sturdy contact and enhance the adsorption energy of
P atoms evidenced by DFT results. In situ Raman and ex situ XRD demonstrate that the final discharge product
of the red P@N-PHCNFs is K4P3.
A one-step synthesis procedure is developed to prepare flexible S Se @carbon nanofibers (CNFs) electrode by coheating S Se powder with electrospun polyacrylonitrile nanofiber papers at 600 °C. The obtained S Se @CNFs film can be used as cathode material for high-performance Li-S batteries and room temperature (RT) Na-S batteries directly. The superior lithium/sodium storage performance derives from its rational structure design, such as the chemical bonding between Se and S, the chemical bonding between S Se and CNFs matrix, and the 3D CNFs network. This easy one-step synthesis procedure provides a feasible route to prepare electrode materials for high-performance Li-S and RT Na-S batteries.
Developing a universal strategy to design piezochromic luminescent materials with desirable properties remains challenging. Here, we report that insertion of a non-emissive molecule into a donor (perylene) and acceptor (1,2,4,5-tetracyanobezene) binary cocrystal can realize fine manipulation of intermolecular interactions between perylene and 1,2,4,5-tetracyanobezene (TCNB) for desirable piezochromic luminescent properties. A continuous pressure-induced emission enhancement up to 3 GPa and a blue shift from 655 to 619 nm have been observed in perylene-TCNB cocrystals upon THF insertion, in contrast to the red-shifted and quenched emission observed when compressing perylene-TCNB cocrystals and other cocrystals reported earlier. By combining experiment with theory, it is further revealed that the inserted non-emissive THF forms blue-shifting hydrogen bonds with neighboring TCNB molecules and promote a conformation change of perylene molecules upon compression, causing the blue-shifted and enhanced emission. This strategy remains valid when inserting other molecules as non-emissive component into perylene-TCNB cocrystals for abnormal piezochromic luminescent behaviors.
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