A composite anode based on intercalation and conversion mechanism for high-rate lithium-ion batteries

Abstract

To increase the specific capacity and cycle stability of lithium-ion batteries at high current density, we have investigated the anode materials. Among them, black phosphorus has attracted attention because of its large theoretical specific capacity (2596 mA h/g). However, the moderate conductivity of black phosphorus itself makes it less effective. The addition of graphite to form P-C and P-O-C bonds with black phosphorus enhances the performance of the battery cell. Lithium ions are primarily stored in black phosphorus-graphite layered structural materials via an intercalation mechanism, which improves electrochemical performance at tiny current density but is inadequate for charge/discharge cycling at high current density. In addition, lithium ions also can undergo conversion mechanism with metal oxide materials (e.g. Tungsten trioxide). While this conversion mechanism enables more stable battery cycling at high current density, the specific capacity remains insufficiently high. Higher charge/discharge specific capacity and long cycle stability of lithium-ion batteries at high current density can be realized by the joint action of the two mechanisms. In this work, black phosphorus, graphite, and tungsten trioxide (BP/G/WO3) composites are prepared by ball milling method. A comprehensive series of electrochemical analyses reveals that the BP/G/WO3-532 electrode (BP, graphite, and WO3 mass ratio of 5:3:2) exhibits the most substantial enhancement in the cycling stability of lithium-ion batteries. The anode exhibits a high specific capacity of 1463.1 mA h/g at 6 A/g and presents a retention capacity of 1159.8 mA h/g after 300 charge/discharge cycles, indicating a high cycle stability and fast reaction kinetics. This result is mainly attributed to the joint action of two mechanisms of composites.