Thermal management systems for high energy density batteries, particularly arrays of such batteries, and methods of making and using thereof are described herein. The system includes one or more thermal conductive microfibrous media with one or more phase change materials dispersed within the microfibrous media and one or more active cooling structures. Energy storage packs or arrays which contain a plurality of energy storage cells and the thermal management system are also described. Further described are thermal or infrared shielding blankets or barriers comprising one or more thermal conductive microfibrous media comprising one or more phase change materials dispersed within the microfibrous media.