Mechanism Study of Carbon Coating Effects on Conversion-Type Anode Materials in Lithium-Ion Batteries: Case Study of ZnMn₂O₄ and ZnO–MnO Composites

Abstract

The carbon coating strategy is intensively used in the modification of conversion-type anode materials to improve their cycling stability and rate capability. Thus, it is necessary to elucidate the modification mechanism induced by carbon coating. For this purpose, bare ZnMn₂O₄, carbon-derivative-coated ZnMn₂O₄, and carbon-coated ZnO-MnO composite materials have been synthesized and investigated in-depth. Herein, high-temperature synchrotron radiation diffraction is used to monitor the phase transition from ZnMn₂O₄ to ZnO-MnO composite during the carbonization process. The electrochemical performance has been evaluated by cyclic voltammetry, galvanostatic cycling, and electrochemical impedance spectroscopy. The carbon- and carbon-derivative-coated samples display well-improved cycling stability in terms of suppressed electrode polarization, a moderate increase in resistance, and slight capacity variation. The influence of carbon coating on the intrinsic conversion process is investigated by ex situ X-ray absorption spectroscopy, which reveals the evolution of Zn and Mn oxidation states. This result confirms that the strong capacity variation of the bare ZnMn₂O₄ is induced not only by the reversible charge storage in the solid electrolyte interphase but also by the phase evolution of active materials. Carbon coating is an effective method to prevent the additional oxidation of MnO to Mn₃O₄, which leads to a stabilization of the main conversion reaction.