Improved lithium insertion/extraction properties of single-walled carbon nanotubes by high-energy ball milling

Abstract

The effects of ball milling on lithium (Li) insertion/extraction properties into/from single-walled carbon nanotubes (SWNTs) were investigated. The SWNTs were synthesized on supported catalysts by thermal chemical-vapor deposition method, purified, and mechanically ball-milled by high-energy ball milling. The purified SWNTs and the ball-milled SWNTs were electrochemically inserted/extracted with Li. The structural and chemical modifications in the ball-milled SWNTs change the insertion/extraction properties of Li ions into/from the ball-milled SWNTs. The reversible capacity (C-rev) increases with increase in the ball milling time, from 616 mAh/g (Li1.7C6) for the purified SWNTs to 988 mAh/g (Li2.7C6) for the ball-milled SWNTs. The undesirable irreversible capacity (C-irr) decreases continuously with increase in the ball milling time, from 1573 mAh/g (Li4.2C6) for the purified SWNTs to 845 mAh/g (Li2.3C6) for the ball-milled SWNTs. The enhanced C-rev of the ball-milled SWNTs is presumably due to a continuous decrease in the Cirr because the SWNTs develop a densely packed structure on the ball milling process. The insertion of Li ions into the ball-milled SWNTs is facilitated by various Li insertion sites formed during the ball milling process in spite of small surface area than the purified SWNTs. Lithium ions inserted into various insertion sites enhance the C-rev in the ball-milled SWNTs with the large voltage hysteresis by hindrance of the extraction of Li ions from the ball-milled SWNTs. In addition, the ball-milled samples exhibit more stable cycle capacities than the purified samples during the charge/discharge cycling.