Cellulose, the most abundant organic polymer on Earth, is a sustainable source of carbon to use as a negative electrode for sodium ion batteries. Here, hard carbons (HC) prepared by cellulose pyrolysis were investigated with varying pyrolysis temperature from 700 degrees C to 1600 degrees C. Characterisation methods such as Small Angle X-ray Scattering (SAXS) measurements and N-2 adsorption were performed to analyse porosity differences between the samples. The graphene sheet arrangements were observed by transmission electron microscopy (TEM): an ordering of the graphene sheets is observed at temperatures above 1150 degrees C and small crystalline domains appear over 1400 degrees C. As the graphene sheets start to align, the BET surface area decreases and the micropore size increases. To correlate hard carbon structures and electrochemical performances, different tests in Na//HC cells with 1 M NaPF6 ethylene carbonate/dimethyl carbonate (EC/DMC) were performed. Samples pyrolysed from 1300 degrees C to 1600 degrees C showed a 300 mAh/g reversible capacity at C/10 rate (where C = 372 mA/g) with an excellent stability in cycling and a very good initial Coulombic efficiency of up to 84%. Furthermore, hard carbons showed an excellent rate capability where sodium extraction rate varies from C/10 to 5 C. At 5 C more than 80% of reversible capacity remains stable for hard carbons synthesized from 1000 degrees C to 1600 degrees C. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.