Hierarchical multi-yolk-shell copper oxide@copper-1, 3, 5-benzenetricarboxylate as an ultrastable anode for lithium ion batteries

Abstract

The capacity attenuation of transition metal oxides (TMOs) and metal–organic frameworks (MOFs) is the obstacle for practical application in lithium ion batteries, due to the extensive volume variation upon charge/discharge cycles. Herein, a hierarchical composite material with copper oxide (CuO) multi-yolks and copper-1, 3, 5-benzenetricarboxylate (Cu-BTC) shell is synthesized by a facile method to study the effect of the hierarchical structure on the electrochemical performance. The porosity and pore volume of CuO@Cu-BTC composites are optimized to buffer the volume change and facilitate the infiltration of electrolytes by altering reaction conditions. The CuO@Cu-BTC (20 h) with the largest surface area and pore volume delivers an excellent reversible capacity of 780.7 mAh g−1 at 200 mA g−1 after 100 cycles, and ultrastable long-term performance with a specific capacity of 569 mAh g−1 at a current density of 1000 mA g−1 after 900 cycles. The corresponding full battery shows moderate capacity retention from 149.4 to 125.8 mAh g−1 after 70 cycles, with a specific capacity retention of 84.2%, based on the mass of lithium iron phosphate (LiFePO4) at 0.2 C (1 C = 170 mA g−1). This strategy applies copper oxide as the metal source of the coordination compound, as well as the internal yolks, which can be extended to the in-situ construction of other hierarchical composites, providing a new avenue for practical application of TMOs and MOFs as anode materials.