Revisiting Lithium- and Sodium-Ion Storage in Hard Carbon Anodes
- Year
- 2023
- Author
- Hoseong Kim, Jong Chan Hyun, Do-Hoon Kim, Jin Hwan Kwak, Jin Bae Lee, Joon Ha Moon, Jaewon Choi, Hee-Dae Lim, Seung Jae Yang, Hyeong Min Jin, Dong June Ahn, Kisuk Kang, Hyoung-Joon Jin*, Hyung-Kyu Lim*, Young Soo Yun*
- Journal
- Advanced Materials
- Vol
- 35
- Page
- 2209128
The galvanostatic lithiation/sodiation voltage profiles of hard carbon anodes are simple, with a sloping drop followed by plateau. However, a precise understanding of the corresponding redox sites and storage mechanisms is still elusive, which hinders further development in commercial applications. In this study, a comprehensive comparison of the lithium- and sodium-ion storage behaviors of hard carbon is conducted, yielding the following key findings: 1) the sloping voltage section is presented by the lithium-ion intercalation in the graphitic lattices of hard carbons, whereas it mainly arises from the chemisorption of sodium-ions on their inner surfaces constituting closed pores, even if the graphitic lattices are unoccupied; 2) the redox sites for the plateau capacities are the same as those for the closed pores regardless of the alkali ions; 3) the sodiation plateau capacities are mostly determined by the volume of the available closed pore, whereas the lithiation plateau capacities are primarily affected by the intercalation propensity; and 4) the intercalation preference and the plateau capacity have an inverse correlation. These findings from extensive characterizations and theoretical investigations provide a relatively clear elucidation of the electrochemical footprint of hard carbon anodes in relation to the redox mechanisms and storage sites for lithium and sodium ions, thereby providing a more rational design strategy for constructing better hard carbon anodes.