Search

Black Phosphorus (BP), a layered structure material with good electrical conductance, has been applied in many occasions and it can be synthesized by many methods including ball milling. However, there lacks a clear understanding about the growth mechanisms. In this paper, we adopt three different ball milling techniques (planetary milling, shake milling and plasma-assisted ball milling) to synthesize BP samples and investigate the mechanism of the formation processes. It is found that BP can be successfully synthesized by all these three ball milling techniques and the (020) orientation is preferential during the milling formation processes. And mechanical energy plays an important role in the conversion process of RP to BP by ball milling. The higher mechanical energy could reduce the milling time and improve crystallinity of the synthesized BP. Furthermore, the huge mechanical energy produced in a short time can form a local high energy intensity area, which is beneficial to the phase transition and formation process. The pressure on the sample powders, formed by the impact between balls and between the balls and the vessel wall, is the main influencing factor affecting the transformation process of RP to BP compared with temperature (additional temperature, not the local temperature generated during the milling process). The synthesized BP based composite presents excellent electrochemical performance as lithium ion battery anode material. This work opens new gateway on facile synthesis of BP for various energy applications.

Few-layer phosphorene (FLP) has attracted strong research interest due to its extraordinary physical and chemical properties. However, an efficient and rapid fabrication of high-quality FLP is still unavailable. Herein, a simple and efficient low melting media-assisted ball milling (LMMBM) approach is developed to prepare FLP in large quantities. The phase change of the LMM at higher temperatures leads to FLP with larger lateral dimensions compared to the ones obtained via dry solid state ball milling. Transmission electron microscope (TEM) studies indicated that liquid facilitates the slipping/curling of black phosphorus (BP) layers under the shearing force generated during ball milling. When used as an anode in Lithium-ion batteries, the FLP-C composite exhibits high initial Coulombic efficiency, stable cycling and rate capacity. This LMMBM approach can be adopted for mass production of other two-dimensional materials from their bulk counterparts.

Owing to the high theoretic capacity (2596 mAh g−1) and suitable lithiation potential (～0.7 V vs. Li+/Li), Black phosphorus (BP) is considered as an ideal anode material for the fast-charging lithium-ion batteries. However, BP still faces the large volume change and low Li+ transfer during the charge/discharge. In this work, a facile two-step high-energy ball milling method is developed to synthesis the black phosphorus@TiP2–C (CBP@TiP2–C) nanocomposite for the high-rate performance anode material, in which the conductive nanocrystalline TiP2 is in-situ introduced and uniformly distributed into BP-C matrix. We reveal that the uniformly dispersed TiP2 nanocrystals can enhance the electronic and ionic conductivities of active particles and the electrode reaction kinetics. The lithiation product cubic LiyTiP4 phase is beneficial to release the stress, reduce the Li+ diffusion energy barrier and accelerate the Li+ extraction from LiP3 upon delithiation. Moreover, the contact among different components can be improved by Ti–C and P–C bonds in the CBP@TiP2–C, thus ensuring excellent electric contact within the material and enhancing the structural stability of composites. As a result, the CBP@TiP2–C anode displays a high reversible capacity of 1007.4 mAh g−1 at 10.0 A g−1 and excellent capacity retention of 925.6 mAh g−1 after 500 cycles at 2 A g−1.

Titanium phosphide (TiP2) is particularly interesting due to its ability to form the stable Li–Ti–P ternary phase. However, TiP2 faces the limitations in cyclic stability due to the volume change occurred by the destruction/recovery of the long-range cubic order Li–Ti–P phase, and unable to deliver high capacity. In this work, we propose the in-situ formation of electrochemically inactive TiP and phosphorus via partial decomposition of TiP2 by ball milling process, achieving a multi-phase TiP2–TiP–P–C composite. On one hand, the decomposition-formed TiP effectively relieve the stress caused by the formation of LixTiP4 and LiP3. On the other hand, another decomposition-formed small-sized phosphorus significantly reduce its volume change during the lithiation/delithiation cycles for the overall capacity. Accordingly, the synthesized multi-phase TiP2–TiP–P–C with the above cooperative effects delivers a high capacity of 836.3 mAh g−1 at 0.2 A g−1 as high-performance Lithium-ion battery anode. In addition, a notable capacity retention of 81.4% is also achieved after 1000 cycles at 5 A g−1. Furthermore, when paired with LiFePO4 cathode in a full cell, the excellent specific capacity, cycling and rate performance can also be obtained. The rational design of TiP2–TiP–P–C will be beneficial towards the future development of metal-phosphide-phosphorous composite as LIB anode.

Aqueous zinc-ion batteries have emerged as prospective energy storage devices to partly replace organic ion batteries due to their high safety and eco-friendliness. Providing multifold synthesis methods of cathode materials is essential for Zn-ion battery development. Here, we demonstrated a practical strategy for the large-scale fabrication of high performance β-MnO2@C hybrid cathode materials by plasma assisted milling (P-milling). After P-milling for 10 h, the porous hybrid microparticles consisted of MnO2 nanocrystallites, which combined and wrapped with the thin carbon layer derived from expanded graphite. The pores among the β-MnO2@C particles facilitated electrolyte infiltration during continuous cycling, while combining with carbon greatly enhanced the conductivity of the hybrids and helped to alleviate MnO2 dissolution. Therefore, the β-MnO2@C hybrids delivered excellent cycle stability, with a high capacity of 130 mAh g−1 for 400 cycles at a current rate of 300 mA g−1 in an aqueous Zn(CF3SO3)2 electrolyte. This capacity retention was amongst the highest reported so far for MnO2-based cathode materials for Zn-ion batteries.

Phosphorus (P)-based materials are recognized as one type of prospective candidate anodes due to its high theoretical capacities. However, it still suffers the relatively low structural stability and rate performance. In the present work, an amorphous ternary black Phosphorus (BP)- Titanium dioxide (TiO2)- Carbon (C) nanocomposite is fabricated by a facile ball milling process, which can serve as a prospective alternative for advanced anode material of Lithium-Ion Battery (LIB). We find that the introduction of TiO2 can effectively improve the conductivities of electron and lithium ion, the electrode reaction kinetics, and stabilize the structural integrity of the active material. What's more, the strong Ti–O–P bonds, forming among TiO2 and BP, can further improve the utilization of active material and the transfer of interfacial electron. As a result, the BP-TiO2-C composite exhibits outstanding electrochemical performance, involving high specific capacity, excellent rate performance (a reversible capacity of 947.4 mA h g−1 at 7.0 A g−1), and stable cycling performance (a capacity of 935.8 mA h g−1 after 300 cycles at 2 A g−1 with 85.3% retention ratio). Furthermore, when this nanocomposite is assembled with LiCoO2 cathode to build a full cell, it can also denote an excellent specific capacity, stable cycling performance and rate performance.