Oxygen Functional Group Modification of Cellulose-Derived Hard Carbon for Enhanced Sodium Ion Storage

作者：Hua Wang, Fei Sun, Zhibin Qu, Kunfang Wang, Lijie Wang, Xinxin Pi, Jihui Gao, Guangbo Zhao · 发表于：ACS Sustainable Chemistry & Engineering · 年份：2019 · DOI：10.1021/acssuschemeng.9b04676 · 被引用次数：147 · 研究领域：Advancements in Battery Materials、Supercapacitor Materials and Fabrication、Advanced Battery Materials and Technologies

Oxygen-containing groups in carbon materials have been demonstrated to be effective in the anodic sodium-ion storage process; however, the effect of specific oxygen-containing groups on the sodium-ion storage in the carbon framework remains to be explored. Based on a mechanochemical process (exemplified by ball milling in the presence of dry ice), a selectively modified cellulose-derived hard carbon (BHC-CO 2 ) with a high oxygen content of 19.33 at. % and carboxyl-dominant groups was prepared in this work. The fabricated BHC-CO 2 anode exhibits excellent electrochemical performance with a high reversible capacity of 293.5 mA h g –1 at a current density of 0.05 A g –1, two times as high as that of the oxygen-deficient BHC-CO 2 -H 2 anode, demonstrating the significant role of oxygen-containing groups in enhancing the Na + storage. Moreover, the BHC-CO 2 anode has an excellent high-rate cycling stability with a specific capacity of 80.0 mA h g –1 even after 2000 cycles at 1 A g –1 . Qualitative analyses of capacitive effect combined with density functional theory calculations further reveal that carboxyl groups introduced by the mechanochemical process facilitate Na + adsorption on the carbon surface, enhancing the capacitive Na + storage process and thus greatly improving the capacity. This work demonstrates the role of carboxyl on Na + storage by carbonaceous materials and provides theoretical guidance for the oxygen functional group modification of carbon materials to enhan...