An in-depth understanding of the thermal behavior of lithium-ion battery materials is valuable for two reasons: one is to devise strategies for inhibiting the risk of catastrophic thermal runaway and the other is to respond to the increasing demand for sustainable batteries using a direct regeneration method. Li1+x[Li1/3Ti5/3]O4 (LTO) is regarded as a suitable negative electrode under the type of severe conditions that cause this thermal runaway, such as in ignition systems for automobiles. Thus, in this study, we used differential scanning calorimetry to systematically analyze lithiated LTO combined with ex situ and in situ high-temperature X-ray diffraction measurements. The observed thermal reactions with a LiPF6-based electrolyte were divided into three processes: (i) the decomposition of the initially formed solid electrolyte interphase below 200 °C, (ii) the formation of a LiF phase at 200 °C ≤ T ≤ 340 °C, and (iii) the formation of a TiO2 phase at T > 340 °C. Because the enthalpy change in process (ii) mainly contributed to the total heat generation, fluorine-free Li salts and/or stabilization of the LTO lattice may be effective in coping with the thermal runaway. Even in various lithiated states, a direct regeneration method returned the discharge capacity of LTO to ∼90% of its initial value, if we ignore the contributions from the electrochemically inactive LiF and TiO2 rutile phases. Hence, it can be concluded that the recycling performance of LTO is far superior to those of lithium transition metal oxides for a positive electrode, whose delithiated states easily convert into electrochemical-inactive phases at high temperatures.
Keywords: lithium titanium oxide; lithium-ion battery; negative electrode; recycling; spinel; thermal runaway.