Structural evolution of LiOH: evidence of a solid–solid transformation toward Li2O close to the melting temperature

The structural evolution of LiOH has been studied between 10 K and 1670 K using a combination of neutron and X-ray diffraction and calorimetric measurements. The room temperature tetragonal phase of LiOH has been observed down to 10 K. Above the room temperature a dehydration of solid LiOH into solid Li2O is observed at a temperature and speed which strongly changes with the thermal history and the partial pressure of water vapour. Depending on these conditions the transformation of LiOH in to Li2O before the fusion temperature can be complete, partial or suppressed. In this latter case, as previously reported in the literature, a first order structural phase transition of LiOH is observed close before the melting temperature; the transformation into Li2O is then observed at this temperature.