Recently, the research team of Yu Xuefeng, a researcher at the Shenzhen Institute of Advanced Technology, Chinese Academy of Sciences, has made new breakthroughs in the field of electrochemical preparation of black phosphorus and its energy storage applications. The related work "Synthesis of High-Quality Black Phosphorus Sponges for All-Solid-State Supercapacitor" ("Preparation of High-Quality Black Phosphorus Sponges for All-Solid-State Supercapacitor") was published in Materials Horizons (DOI) : 10.1039 / c8mh00708j). The co-first author of the paper is Wen Min, a postdoctoral fellow in the research group, and Liu Danni, a research assistant, and the corresponding author is Yu Xuefeng.

As a new type of two-dimensional layered material, black phosphorus has been widely used in physics, chemistry, material science and other fields in recent years. The characteristics of large specific surface area, high carrier mobility, and good mechanical strength have attracted wide attention in the field of energy storage and conversion. Constructing a three-dimensional structure with two-dimensional sheet materials as the basic elements is generally regarded as an effective way to improve the energy storage performance of the material. However, the sensitivity of two-dimensional black phosphorus to air, water and oxidants poses a huge challenge to the construction of three-dimensional black phosphorus structures. Therefore, it is of great scientific significance and application prospect to study an effective method to construct a new type of three-dimensional black phosphorus structure with excellent performance.

In this study, the research team achieved an efficient and high-quality preparation of three-dimensional black phosphorus sponge by electrochemical methods. The preparation method is simple and fast, and can be completed in an air environment at normal temperature and pressure, and the time only takes 3 minutes (Figure 1). By designing the structure of the electrolytic cell and selecting the intercalated ion, counter ion and electrolyte system with appropriate size, the scientific researcher overcomes the problems of time-consuming, easy oxidation, and easy fracture of the layer that black phosphorous often faces, and successfully prepares high quality , Semi-crosslinked three-dimensional black phosphorus sponge. Scanning electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, transmission electron microscopy, atomic force microscopy, and theoretical simulation results all show that the three-dimensional black phosphorus sponge is composed of ultra-large, ultra-thin, unoxidized high-quality two-dimensional phosphorene units, of which There is no lack of a single layer of phosphene. These phosphene elements are half-crosslinked to form a three-dimensional black phosphorus sponge (Figure 2). Researchers have prepared all-solid supercapacitors using this three-dimensional black phosphorus sponge as the electrode material, showing excellent supercapacitor performance and stability. At a scanning speed of 10 mv / s, the specific capacitance of the capacitor reaches 80 F / g, which is much higher than that of a capacitor using two-dimensional black phosphorus nanosheets and bulk black phosphorus as electrode materials. After 15,000 charge-discharge cycles, the capacity only declined by 20% (Figure 3).

The research work was supported by the Chinese Academy of Sciences' Frontier Science Research Key Program, the National Natural Science Foundation of China, and the Hong Kong Research Grants Fund.

Figure 1. Schematic diagram of the preparation process of three-dimensional black phosphorus

Figure 2. Scanning electron micrographs of three-dimensional black phosphorus (a, b); Raman spectrum (c) and XPS spectrum (d) of three-dimensional black phosphorus and bulk black phosphorus

Figure 3. Schematic diagram of the preparation of an all-solid-state supercapacitor (a), the cv curve at different sweep speeds (b), the change of specific capacity with sweep speed (c), the GCD curve (d), the stability test Figure (e)

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