A 3D graphitic foam vertically aligned graphitic structure and a low density of defects is derived through chloroaluminate anion intercalation of graphite followed by thermal expansion and electrochemical hydrogen evolution. Such aligned graphitic structure affords excellent Al-ion battery characteristics with a discharge capacity of approximate to 60 mA h g(-1) under a high charge and discharge current density of 12 000 mA g(-1) over approximate to 4000 cycles.