Lithium ion batteries are provided that include materials that provide advantageous endothermic functionalities contributing to the safety and stability of the batteries. The endothermic materials may include a ceramic matrix incorporating an inorganic gas-generating endothermic material. If the temperature of the lithium ion battery rises above a predetermined level, the endothermic materials serve to provide one or more functions to prevent and/or minimize the potential for thermal runaway, e.g., thermal insulation (particularly at high temperatures); (ii) energy absorption; (iii) venting of gases produced, in whole or in part, from endothermic reaction(s) associated with the endothermic materials, (iv) raising total pressure within the battery structure; (v) removal of absorbed heat from the battery system via venting of gases produced during the endothermic reaction(s) associated with the endothermic materials, and/or (vi) dilution of toxic gases (if present) and their safe expulsion from the battery system.