Layer‐Tunable Phosphorene Modulated by the Cation Insertion Rate as a Sodium‐Storage Anode

Abstract

Liquid phase exfoliation of few-layer phosphorene (FL-P) is extensively explored in recent years. Nevertheless, their deficiencies such as ultralong sonication time, limited flake size distribution, and uncontrollable thicknesses are major hurdles for the development of phosphorene-based materials. Herein, electrochemical cationic intercalation has been introduced to prepare phosphorene, through which large-area FL-P without surface functional groups can be efficiently attained (less than 1 h). More importantly, its layer number (from 2 to 11 layers) can be manipulated by changing the applied potential. The as-obtained phosphorene delivers superior sodium-storage performances when directly utilized as an anode material in sodium-ion batteries. This electrochemical cation insertion method to prepare phosphorene should greatly facilitate the development of phosphorene-based technologies. Moreover, this work provides the possibility for the scalable preparation of monolayer 2D materials by exploring intercalation ions. Additionally, the successful electrochemical exfoliation of phosphorene can promote the application of electrochemical exfoliation in other 2D materials.

Initiating Hexagonal MoO3 for Superb‐Stable and Fast NH4+ Storage Based on Hydrogen Bond Chemistry

“…Nonmetallic cations, e.g., proton (H + ), hydronium (H 3 O + ), and ammonium (NH 4 + ) ions, have rarely been regarded as charge carriers in aqueous battery chemistry for research and commercial applications, [ 1–3 ] where the mainstream attention located at the metal cations, such as Li + , Na + , Zn 2+ , and Al 3+ ions. [ 4–8 ] Most recently, Ji and co‐workers have pioneeringly reported several typical aqueous batteries utilizing H + and NH 4 + as charging carriers with outstanding electrochemical performance, especially for the ultrafast kinetics with high power density. [ 1,9 ] It could be ascribed to (1) nondiffusion‐controlled topochemistry between nonmetallic charging carriers and electrode framework during insertion/extraction process, resulting in pseudocapacitive‐dominated behavior; [ 1,9 ] (2) the lower molar mass and smaller hydrated ionic size of such non‐metallic charging carriers, which could result in fast diffusion in aqueous electrolytes.…”

Emerging 2D Materials Produced via Electrochemistry

“…TBA + cations and many organic solvents, such as DMF, PC, dimethyl sulfoxide (DMSO) have been studied in this system. For example, Huang et al produced few‐layer crystalline phosphorene sheets in anhydrous DMF dissolved with 0.5 m tetrabutylammonium hexafluorophosphate (TBA PF 6 ) . The modulation of working potential (from −2.5 to −15 V) could control the intercalation process of TBA + cations.…”

Rational Assembly of Hollow Microporous Carbon Spheres as P Hosts for Long‐Life Sodium‐Ion Batteries

“…[16][17][18] In view of the abovementioned reasons, it is crucial to identify anode materials that possess high capacities and long cyclic stability in SIBs. [26,27] Red P presents better chemical stability at room temperature and is commercially available at lower cost than other phosphorus allotropes, like white P, black P, [28] and violet P. [29] Nevertheless, most electrodes made from red P suffered low rate capacities, severe capacity reduction, and poor electrochemical reversibility, [19,21,30] which hindered the wide application of red P-based anodes. [26,27] Red P presents better chemical stability at room temperature and is commercially available at lower cost than other phosphorus allotropes, like white P, black P, [28] and violet P. [29] Nevertheless, most electrodes made from red P suffered low rate capacities, severe capacity reduction, and poor electrochemical reversibility, [19,21,30] which hindered the wide application of red P-based anodes.…”