Improved electrode kinetics in lithium manganospinel nanoparticles synthesized by hydrothermal methods: identifying and eliminating oxygen vacancies

Abstract

Lithium-rich manganospinel (Li₁₊xMn_2–xO_4–δ, lithium manganese oxide) has been synthesized by hydrothermal methods employing potassium permanganate, lithium hydroxide, and acetone as synthons. The solid product crystallizes as 30–50 nm particles with some larger 100–300 nm particles also occurring. Materials prepared by this low-temperature route contain oxygen vacancies which can be demonstrated by combining thermogravimetric analysis, differential scanning calorimetry, and cyclic voltammetry. Oxygen vacancies can be minimized beyond the limits of detection for these experiments by annealing the compound in air at 500 °C for 4 h. At room temperature, Rietveld refinement of the powder neutron diffraction pattern shows an orthorhombic Fddd(α00) superlattice of the Fdm space group for hydrothermally synthesized lithium manganospinel. After annealing, oxygen vacancies are eliminated and the superlattice features disappear. Furthermore, the hydrothermal synthesis of lithium manganospinel performed under a pure oxygen atmosphere followed by annealing at 500 °C for 4 h in air gives superior electrochemical properties. This compound shows a reversible capacity of 115 mAh/g when cycled at a rate C/3 and retains 93.6% of this capacity after 100 cycles. This same capacity is observed at the faster rate of 3C. At 5C, the capacity drops to 99 mAh/g, but capacity retention remains greater than 95% after 100 cycles. Finally, when cycled at 5C at an elevated temperature of 55 °C, the O₂ annealed sample shows an initial capacity of 99 mAh/g with 89% capacity retention after 100 cycles. The high rate capability of this material is ascribed to fast lithium-ion diffusion, estimated to be 10⁻⁷ to 10⁻⁹ cm² s⁻¹ by electrochemical impedance spectroscopy.