High Capacity of Hard Carbon Anode in Na-Ion Batteries Unlocked by PO_x Doping

The capacity of hard carbon anodes in Na-ion batteries rarely reaches values beyond 300 mAh/g. We report that doping PO x into local structures of hard carbon increases its reversible capacity from 283 to 359 mAh/g. We confirm that the doped PO x is redox inactive by X-ray adsorption near edge structure measurements, thus not contributing to the higher capacity. We observe two significant changes of hard carbon’s local structures caused by doping. First, the (002) d -spacing inside the turbostratic nanodomains is increased, revealed by both laboratory and synchrotron X-ray diffraction. Second, doping turns turbostratic nanodomains more defective along ab planes, indicated by neutron total scattering and the associated pair distribution function studies. The local structural changes of hard carbon are correlated to the higher capacity, where both the plateau and slope regions in the potential profiles are enhanced. Our study demonstrates that Na-ion storage in hard carbon heavily depends on carbon local structures, where such structures, despite being disordered, can be tuned toward unusually high capacities.