Composite Electroforming of a Binder-Free Porous Ni/S-PTh Electrode for Li–S Batteries by Combining 3D Printing, Pulse Plating, and Composite Electrodeposition

A novel process for the synthesis of binder-free, porous nickel/polythiophene-functionalized sulfur (Ni/S-PTh) composite cathodes for lithium–sulfur (Li–S) batteries is introduced in this paper. Initially, a polyvinyl butyl polymer scaffold is 3D printed, then coated with a graphite-based conducting layer, and, finally, it is pulse-plated for nickel deposition to produce a high-surface-area, mechanically stable current collector. S-PTh particles are afterwards co-deposited into the Ni matrix through composite electrodeposition. After the dissolution of the polymer template, the resulting self-standing electrodes still maintain porous structure with uniform sulfur distribution and a distinct transition between the dense Ni layer and the Ni/S-PTh composite layer. Electrochemical characterization of the Ni/S-PTh composite cathodes by galvanostatic cycling at C/10 rate results in an initial specific discharge capacity of ~1120 mAh·g−1 and a specific capacity of ~910 mAh·g−1 after 200 cycles, resulting in a high capacity retention of ~81 %. For our novel approach, no steps at high temperatures or toxic solvents are involved and the need for polymer binders and conductive additives is avoided. These results demonstrate the potential of composite electrodeposition in combination with 3D printing for producing sustainable, high-performance sulfur cathodes with tunable architecture.