Lithium Attachment to C60 and Nitrogen- and Boron-Doped C60: A Mechanistic Study

Fullerene-based materials including C₆₀ and doped C₆₀ have previously been proposed as anodes for lithium ion batteries. It was also shown earlier that n- and p-doping of small molecules can substantially increase voltages and specific capacities. Here, we study ab initio the attachment of multiple lithium atoms to C₆₀, nitrogen-doped C₆₀ (n-type), and boron doped C₆₀ (p-type). We relate the observed attachment energies (which determine the voltage) to changes in the electronic structure induced by Li attachment and by doping. We compare results with a GGA (generalized gradient approximation) functional and a hybrid functional and show that while they agree semi-quantitatively with respect to the expected voltages, there are qualitative differences in the electronic structure. We show that, contrary to small molecules, single atom n- and p-doping will not lead to practically useful modulation of the voltage-capacity curve beyond the initial stages of lithiation.