Evidence of solid-solution reaction upon lithium insertion into cryptomelane K0.25Mn2O4 material

Abstract

Cryptomelane-type K0.25Mn2O4 material is prepared via a template-free, one-step hydrothermal method. Cryptomelane K0.25Mn2O4 adopts an I4/m tetragonal structure with a distinct tunnel feature built from MnO6 units. Its structural stability arises from the inherent stability of the MnO6 framework which hosts potassium ions, which in turn permits faster ionic diffusion, making the material attractive for application as a cathode in lithium-ion batteries. Despite this potential use, the phase transitions and structural evolution of cryptomelane during lithiation and delithiation remain unclear. The coexistence of Mn3+ and Mn4+ in the compound during lithiation and delithiation processes induces different levels of Jahn–Teller distortion, further complicating the lattice evolution. In this work, the lattice evolution of the cryptomelane K0.25Mn2O4 during its function as a cathode within a lithium-ion battery is measured in a customized coin cell using in situ synchrotron X-ray diffraction. We find that the lithiation–delithiation of cryptomelane cathode proceeds through a solid-solution reaction, associated with variations of the a and c lattice parameters and a reversible strain effect induced by Jahn–Teller distortion of Mn3+. The lattice parameter changes and the strain are quantified in this work, with the results demonstrating that cryptomelane is a relatively good candidate cathode material for lithium-ion battery use. © 2014, American Chemical Society.