Heather N. Emady

Solvent‐ and polymer‐binder‐free fabrication of sulfur positive electrode by heat‐roll‐pressed powder‐bed lamination relies on sulfur–carbon (S/C) composites in which sulfur must function as both active material and a thermally activated binding phase. Yet, how intraparticle sulfur distribution governs powder‐bed consolidation and the durability of the resulting electrode film remains unclear. Here, we compare two S/C composites with identical sulfur content (∼70 wt.%) but contrasting architectures, a ball‐milled composite (B‐S/C) with surface‐aggregated sulfur and a melt‐infiltrated composite (T‐S/C) with uniformly confined sulfur in a porous carbon framework. Structural and rheological analyses reveal that the B‐S/C, containing larger sulfur aggregates, exhibits higher cohesion and compressibility, which is favorable for interparticle bonding, yet forms sulfur‐depleted rims and crack‐prone crusts during heat‐roll pressing. In contrast, uniformly confined sulfur in T‐S/C enables cohesive interparticle fusion into a continuous porous network. Electrochemically, T‐S/C electrodes deliver improved rate capability and durable cycling in both coin‐type and pouch‐type Li/S batteries, markedly outperforming B‐S/C‐based Li/S batteries. These results establish homogeneous intraparticle sulfur distribution as a key design rule to preserve porosity during dry compaction and enable reliable manufacturing of high‐performance polymer‐binder‐free sulfur positive electrodes for lithium/sulfur batteries.