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• Zn-substituted Co 3 O 4 microspheres with a rough surface are synthesized. • Zn substitution modifies the lithium storage mechanism of Co 3 O 4 anodes. • The optimized sample exhibits good performance within half and full cells. Substituting Co 3 O 4 submicron spheres with Zn ions modifies the lithium storage mechanism, leading to an enhanced electrochemical performance. [Display omitted] Carbonaceous materials are used as the anode for rechargeable lithium-ion batteries (LIBs), however, lithium dendrites are easily formed during cycling due to the low lithium insertion potential (~0.1 V versus Li+/Li). As alternative anodes, transition metal oxides based on conversion mechanism have attached much attention. But the high lithiation potential (>1.0 V vs. Li+/Li) usually leads to a low output voltage and energy density when used in a full cell configuration. Herein, Zn-substituted Co 3 O 4 submicron spheres are successfully synthesized by a facile solvothermal reaction and subsequent calcination method. When used as the anode for LIB, the optimized sample shows a specific capacity of 686 mAh g−1 at 0.8 A g−1 after 500 cycles, and a specific capacity of 692.9 mAh g−1 at a higher current density of 3.2 A g−1 in a half-cell. Thanks to the controlled Zn substitution, the discharge voltage plateau is 0.16 V lower than that of the pure Co 3 O 4 anode at a current density of 0.4 A g−1. Further investigation of the 0.5Zn-Co 3 O 4 //LiCoO 2 full cells also displays a high capacity (400.7 mAh g−1 after 200 cycles at 0.4 A g−1) and an excellent rate capability (658.1 mAh g−1 at 1.6 A g−1) compared with the Co 3 O 4 //LiCoO 2 full cells. This work confirms that substituting suitable metal elements into sub-micron conversion based anodes can reduce the voltage plateau, which is of great significance for the practical applications in high performance energy storage devices. [ABSTRACT FROM AUTHOR]