Copper sulfides for rechargeable lithium batteries: Linking cycling stability to electrolyte composition

Copper sulfides are attractive electrode materials as their reaction with lithium offers high capacity and energy density. However, the reversibility is poor and (nano)structuring is considered necessary to achieve moderate improvements. In contrast, we show in this study that the electrolyte is a major factor that governs the reversibility of the cell reaction. All our experiments were done with commercially available copper sulfides (CuS and Cu2S) without any special nanostructure. Different electrolyte compositions were tested among LiPF6 in EC/DMC and LiTFSI in DOL/DME. While rapid capacity fading is found in cells containing carbonate-based electrolytes, cells with ether-based electrolytes show a much better electrochemical performance. For a mixture of 1 M LiTFSI in DOL/DME, Cu2S can be cycled with capacities of around 200 mAh g−1 for more than 150 cycles with coulombic efficiencies >98.4%, for example. The improved stability in the ether-based electrolyte further allowed us to study how the discharge and charge voltage change during prolonged cycling. Our study underlines that improvements in the Li/CuS and Li/Cu2S system are still possible by very simple measures, but further studies on the complex Li-Cu-S phase behavior are necessary to understand the discharging and especially the charging mechanisms.