Insight of the thermal characteristics and potential flame spread over lithium-ion battery (LIB) modules is important for designing battery thermal management system and fire protection measures. Such thermal characteristics and potential flame spread are also dependent on the different anode and cathode materials as well as the electrolyte. In the present study, thermal behavior and flame propagation over seven 50 A h Li(Ni1/3Mn1/3CO1/3)O-2/Li(4)TisO(12) large format LIBs arranged in rhombus and parallel layouts were investigated by directly heating one of the battery units. Such batteries have already been used commercially for energy storage while relatively little is known about its safety features in connection with potential runaway caused fire and explosion hazards. It was found in the present heating tests that fire-impingement resulted in elevated temperatures in the immediate vicinity of the LIBs that were in the range of between 200 degrees C and 900 degrees C. Such temperature aggravated thermal runaway (TR) propagation, resulting in rapid temperature rise within the battery module and even explosions after 20 min of "smoldering period". The thermal runaway and subsequent fire and explosion observed in the heating test was attributed to the violent reduction of the cathode material which coexisted with the electrolyte when the temperature exceeded 260 degrees C. Separate laboratory tests, which measured the heat and gases generation from samples of the anode and cathode materials using C80 calorimeter, provided insight of the physical-chemistry processes inside the battery when the temperature reaches between 30 degrees C and 300 degrees C. The self-accelerating decomposition temperature of the cell, regarded as the critical temperature to trigger TR propagation, was calculated as 126.1 and 139.2 degrees C using the classical Semenov and Frank-Kamenetskii models and the measurements of the calorimeter with the samples. These are consistent with the measured values in the heating tests in which TR propagated. The events leading to the explosions in the test for the rhombus layout was further analyzed and two possible explanations were postulated and analyzed based on either internal catalytic reactions or Boiling Liquid Expansion Vapor Explosion (BLEW). (C) 2016 Elsevier Ltd. All rights reserved.