Abstract
Hard carbon is the candidate anode material for the commercialization of Na-ion batteries — the batteries that by virtue of being constructed from inexpensive and abundant components open the door for massive scale up of battery-based storage of electrical energy. Holding back the development of these batteries is that a complete understanding of the mechanism of Na-ion storage in hard carbon has remained elusive. Although as an amorphous carbon, hard carbon possesses a subtle and complex structure composed of domains of layered rumpled sheets that have local order resembling graphene within each layer but complete disorder along the c-axis between layers. This article presents two key discoveries: first that characteristics of hard carbon’s structure can be modified systematically by heteroatom doping, and second, that these changes greatly affect Na-ion storage properties, which reveal the mechanisms for Na storage in hard carbon. Specifically, P, S and B doping was used to engineer the density of local defects in graphenic layers, and to modify the spacing between the layers. Opening the interlayer spacing through P or S doping extends the low-voltage capacity plateau, while increasing the defect concentration with P or B doping leads to high first sodiation capacity. We further observe that the highly defective B-doped hard carbon suffers a tremendous irreversible capacity in the first desodiation cycle. Our combined first principles calculations and experimental studies revealed a new trapping mechanism, showing that the high binding energies between B-doping induced defects and Na-ions are responsible for the irreversible capacity. The understanding generated in this work provides a totally new set of guiding principles for materials engineers working to optimize hard carbon for Na-ion battery applications.
