Pseudocapacitive Lithium Storage of Cauliflower-Like CoFe₂ O₄ for Low-Temperature Battery Operation

Binary transition-metal oxides (BTMOs) with hierarchical micro-nano-structures have attracted great interest as potential anode materials for lithium-ion batteries (LIBs). Herein, we report the fabrication of hierarchical cauliflower-like CoFe₂ O₄ (cl-CoFe₂ O₄ ) via a facile room-temperature co-precipitation method followed by post-synthetic annealing. The obtained cauliflower structure is constructed by the assembly of microrods, which themselves are composed of small nanoparticles. Such hierarchical micro-nano-structure can promote fast ion transport and stable electrode-electrolyte interfaces. As a result, the cl-CoFe₂ O₄ can deliver a high specific capacity (1019.9 mAh g^-1 at 0.1 A g^-1 ), excellent rate capability (626.0 mAh g^-1 at 5 A g^-1 ), and good cyclability (675.4 mAh g^-1 at 4 A g^-1 for over 400 cycles) as an anode material for LIBs. Even at low temperatures of 0 °C and -25 °C, the cl-CoFe₂ O₄ anode can deliver high capacities of 907.5 and 664.5 mAh g^-1 at 100 mA g^-1 , respectively, indicating its wide operating temperature. More importantly, the full-cell assembled with a commercial LiFePO₄ cathode exhibits a high rate performance (214.2 mAh g^-1 at 5000 mA g^-1 ) and an impressive cycling performance (612.7 mAh g^-1 over 140 cycles at 300 mA g^-1 ) in the voltage range of 0.5-3.6 V. Kinetic analysis reveals that the electrochemical performance of cl-CoFe₂ O₄ is dominated by pseudocapacitive behavior, leading to fast Li⁺ insertion/extraction and good cycling life.