The phase transition of Li₃PO₄ solid electrolyte for secondary batteries in vacuum has been studied by using real-time synchrotron X-ray scattering. According to the vacuum heating results, the crystal β-Li₃PO₄ phase was stable only from room temperature to 400°C. The crystal γ-Li₃PO₄ phase appeared at 410°C and the crystal β-Li₃PO₄ phase completely disappeared at 430°C. The transition from the β-Li₃PO₄ to the γ-Li₃PO₄ phases occurred primarily at 410°C, which is 40°C lower than the transition temperature of 450°C in air. The decrease in the phase transition temperature in vacuum, compared to that in air, is attributed to a relatively high concentration of oxygen vacancies. As the isothermal annealing time at 390°C was increased to 8 hours, the β-Li₃PO₄ phase was completely transitioned into the γ-Li₃PO₄ phase. Our study revealed the detailed transition behavior from the β-Li₃PO₄ to the γ-Li₃PO₄ phases during real-time annealing in vacuum.

We have studied the thermal stability of NCM622 cathode material for Li-ion batteries using real-time synchrotron x-ray scattering below 600°C in both air and vacuum. The expansion of the mean particle size, which reached maximum values of 10.3 μm in air and 10.6 μm in vacuum at 200°C, was attributed to the dehydration of intergranular water within the NCM622 powders. Across all annealing temperatures, the amount of crystal NCM622 phase in air was consistently higher than that in vacuum. The crystal domain sizes in air showed less variation than that in vacuum during annealing from RT to 500°C. These indicate that the crystal NCM622 phase is more thermally stable during annealing in air than in vacuum. This stability is attributed to the presence of 21% oxygen in air, which is absent under vacuum conditions.

Citations

• Role of surface vibration modes in Si nanocrystals within light emitting porous Si at the strong confinement regime
  M. Mahdouani, S. Gardelis, A. G. Nassiopoulou
  Journal of Applied Physics.2011;[Epub]     CrossRef